Synthesis of novel naphth[1,2-f][1,4]oxazepine-3,4-dione heterocycles

Article abstract of DOI:10.1002/jhet.166

(Chemical Equation Presented) A number of N-heteroaryl aminonaphthols (Betti bases) were prepared from the reaction of 2-naphthol, 3-aminopyridine, and aromatic aldehydes. Subsequent condensation of the prepared Betti bases with oxalyl chloride afforded t

Full text of DOI:10.1002/jhet.166

914
Synthesis of Novel Naphth[1,2-f][1,4]oxazepine-3,4-dione
Heterocycles
Vol 46
Mehdi Ghandi,a* Abolfazl Olyaei,b and Saeed Raoufmoghaddama
aSchool of Chemistry, University College of Science, University of Tehran, Tehran, Iran
bDepartment of Chemistry, Payame Noor University (PNU), Qazvin, Iran
*E-mail: ghandi@khayam.ut.ac.ir
Received January 3, 2009
DOI 10.1002/jhet.166
Published online 2 September 2009 in Wiley InterScience (www.interscience.wiley.com).
A number of N-heteroaryl aminonaphthols (Betti bases) were prepared from the reaction of 2-naph-
thol, 3-aminopyridine, and aromatic aldehydes. Subsequent condensation of the prepared Betti bases
with oxalyl chloride afforded the novel naphth[1,2-f][1,4]oxazepine-3,4-dione heterocycles in moderate
to high yields.
J. Heterocyclic Chem., 46, 914 (2009).
INTRODUCTION
ration of oxazepinedione derivatives by lactonization of
some amides obtained from condensation of either 2-
acetoxybenzoic acid chloride or the proper acethoxy-
naphthonic acid chloride with cyclic amino acids [17].
Oxazepine derivatives were described as effective prote-
ase inhibitors [18], integrin antagonists, squalene syn-
thase [19], reverse transcriptase inhibitors [20], and anti-
histamines, which can be used for the efficient therapy
of some allergic and dermatological infections [21]. To
the best of our knowledge, synthesis of dioxo-1,4-naph-
thoxazepine via condensation of aminonaphthols (Betti
bases) with oxalyl chloride has not been previously
reported in literature.
Although Betti’s classical procedure for the prepara-
tion of 1-(a-aminobenzyl)-2-naphthol (Betti base) was
published more than a century ago [1], the possibilities
of the application of this versatile synthon in the ring-
closure reactions to give naphthalene-condensed hetero-
cyclic derivatives have not been thoroughly investigated.
A few publications that have been appeared on this
topic focus on the transformation reactions of the Betti
base analog aminonaphthols with phosgene, ethyl benzi-
midate, 2-carboxybenzaldehyde, levulinic acid, salicylal-
dehyde/acetaldehyde, salicylaldehyde/formalin, benzal-
dehyde derivatives, and bis-aldehydes/NaBH3CN to
naphthoxazine derivatives [2–6]. Traditionally, the Betti
base derivatives synthesis is carried out in organic sol-
vents, such as, EtOH, MeOH, and Et2O, at room tem-
perature for long time or thermally under solvent-less
conditions. As such, utilization of environmental
friendly water as solvent not only provides the product
in an easy work-up procedure but also is in accord with
green sustainable chemistry principles [7–13].
Our very recently reported results on the successful
uncatalyzed quantitative preparation of aminonaphthols
(Betti bases) via one-pot three-component reaction of 2-
naphthol, aromatic aldehydes, and heteroaryl amines,
such as 2-aminopyrimidine, 2-aminopyrazine, and 2-
aminopyridine [22] prompted us to utilize these bases in
the synthesis of the novel dioxo-1,4-naphthoxazepines.
There are many methods for the synthesis of oxaze-
pine ring systems [14]. In the reported synthetic
approaches to the aryl-fused derivatives of 1,4-oxaze-
pines, several bifunctional keto acids were used in Ugi
condensation reaction [15]. Similarly, a number of 1,4-
benzoxazepin-3-ones were obtained via Ugi three-
component condensations using bifunctional starting
materials containing aldehyde and carboxylic acid [16].
A synthetic procedure was also developed for the prepa-
RESULTS AND DISCUSSION
Condensation of Betti bases containing the heteroar-
yls, such as 2-aminopyrimidine, 2-aminopyrazine, and
2-aminopyridine with oxalyl chloride failed to produce
any product with the oxazepinedione structure. It was
concluded that the Betti bases containing the very poor
electron nature of 2-aminopyrimidine, 2-aminopyrazine,
and 2-aminopyridine might have been responsible for
C
V
2009 HeteroCorporation

September 2009
Synthesis of Novel Naphth[1,2-f][1,4]oxazepine-3,4-dione Heterocycles
915
Scheme 1
Identification of 2a–g was carried out on the basis of
spectroscopic information and elemental analysis. The
1H NMR spectra of compounds 2a–g show a sharp sin-
glet for the hydroxyl group at d 10.2 ppm, a doublet for
NH proton at d 6.7 ppm, and a doublet for methine pro-
ton at d 6.5 ppm. D2O is traditionally added into the
NMR tube of compounds containing the OH or NH
group to find the relevant signals and their coupling
effects. Upon addition of D2O into the 2a NMR sample
tube, the d 10.2 ppm and d 6.7 ppm signals disappeared
and the proton of methine located at d 6.5 ppm moiety
collapsed into a singlet. The IR spectra of compounds
2a–g display two absorption bands at 3373–3406 cmꢁ1
for OH and NH groups. Compounds 2a–g exhibit the
expected parent ion peaks with medium intensity in the
Mass spectra.
When the newly synthesized N-heteroaryl-substituted
aminonaphthols 2a–g were treated with oxalyl chloride
in the presence of pyridine in dry 1,2-dichloroethane as
solvent, the corresponding novel naphthoxazepine-
condensed 1,4-naphthoxazepine-3,4-diones 3a–g were
obtained (Scheme 2).
the lack of expected reactivity. Therefore, it was decided
to prepare the Betti bases obtained from one-pot con-
densation of 3-aminopyridine, 2-naphthol with different
aromatic aldehydes. These aminonaphthols containing
the 3-aminopyridine moiety with partially less electron
deficiency with respect to the previously prepared heter-
oaryl amines were expected to successfully furnish the
relevant oxazepine derivatives.
Identification of 3a–g was carried out on the basis of
1H NMR, 13C NMR, IR, Mass spectra, and elemental
1
analysis. The absence of OH and NH protons in the H
NMR and IR spectra confirms the transformation of the
starting aminonaphthols into the products by bonding of
the oxalyl chloride sp2 carbons to the hydroxyl and N-
substituted groups. IR absorption bands appearing at
1633 and 1725 cmꢁ1 reveals the presence of lactam and
lactone carbonyl groups, respectively. The oxazepine-
dione ring methine proton appears as a singlet at d 6.5
ppm and the other protons are displayed in the aromatic
regions. Mass spectra of 3a–g reveal the presence of the
molecular ion peaks and other fragments consistent with
the assigned structures.
As the model reaction, the one-pot reaction of benzal-
dehyde, 2-naphthol, and 3-aminopyridine was carried
out under our previously reported conditions. It was
found that at least 2 h is needed for reaction to be com-
pleted at room temperature. The best result was obtained
at 50ꢀC, because the reaction was completed during 5
min. Therefore, three-component reactions of 2-naph-
thol, 3-aminopyridine, and aromatic aldehydes 1a–g in
water afforded aminonaphthol derivatives 2a–g with
excellent yields (Scheme 1). Reaction times and yields
of the synthesized Betti base derivatives 2a–g are pre-
sented in Table 1.
In summary, we have successfully developed a fast,
convenient, and efficient method for the synthesis of
new N-substituted-aminonaphthol (Betti base) deriva-
tives in water. When compared with other previously
reported procedures in literatures, this method with the
advantages, such as omitting organic solvent, generality
Table 1
Reaction times, yields, and melting points of the products 2 in H2O.
Compound
Aldehyde
Time (min)
Mp (ꢀC)
Yield (%)
2a
2b
2c
2d
2e
2f
Benzaldehyde
5
25
30
50
55
10
15
187–189
157–159
144–145
162–164
149–150
179–180
190–192
90
92
91
95
94
97
93
4-Chlorobenzaldehyde
3-Chlorobenzaldehyde
4-Bromobenzaldehyde
3-Bromobenzaldehyde
4-Nitrrobenzaldehyde
3-Nitrrobenzaldehyde
2g
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

916
M. Ghandi, A. Olyaei, and S. Raoufmoghaddam
Vol 46
Scheme 2
138.11, 143.11, 145.44, 153.88 ppm; ms: m/z (%) 326 (10)
[Mþ], 231 (100), 202 (50), 94 (40). Anal. Calcd for
C22H18N2O: C, 80.98; H, 5.52; N, 8.58%. Found: C, 80.87; H,
5.60; N, 8.49%.
1-(4-Chlorophenyl(pyridine-3-ylamino)methyl)naphthalene-
2-ol (2b). IR (potassium bromide): 3373, 3051, 2917, 1627,
1
1299, 806 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.60 (d, J
¼ 6.6 Hz, 1H, methine-H), 6.72 (d, J ¼ 6.6 Hz, 1H, NH),
7.02–8.12 (m, 14H, NPh-H, Ph-H, and Pyridine-H), 10.25 (s,
1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): d 52.86,
119.07, 119.21, 119.26, 123.33, 124.36, 124.69, 127.08,
128.99, 129.42, 129.51, 129.66, 130.39 131.83, 132.95,
136.76, 138.26, 142.27, 145.27, 153.85 ppm; ms: m/z (%) 360
(15) [Mþ], 265 (90), 231 (100), 202 (50), 144 (15), 94 (30).
Anal. Calcd for C22H17ClN2O: C, 73.23; H, 4.71; N, 7.76%.
Found: C, 73.19; H, 4.64; N, 7.80%.
and simplicity of procedure, lower reaction time, elimi-
nation of acid catalyst, and obtaining excellent yields
are worth noting. Moreover, we have developed a con-
venient synthetic strategy to novel naphthoxazepine-con-
densed derivatives 1,4-naphthoxazepine-3,4-diones. To
the best of our knowledge, the synthesis of seven-mem-
bered rings consisting of 1,4-naphthoxazepine-3,4-diones
have not been previously reported.
1-(3-Chlorophenyl(pyridine-3-ylamino)methyl)naphthalene-
2-ol (2c). IR (potassium bromide): 3404, 3051, 2906, 1625,
1
1292, 815 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.57 (d, J
¼ 6.8 Hz, 1H, methine-H), 6.74 (d, J ¼ 6.8 Hz, 1H, NH),
7.02–8.13 (m, 14H, NPh-H, Ph-H, and Pyridine-H), 10.28 (s,
1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): d 52.97,
119.10, 119.17, 119.24, 123.39, 124.37, 124.52, 126.29,
127.15, 127.23, 127.32, 129.55, 129.61, 130.48, 130.96,
132.93, 133.81, 136.77, 138.35, 145.16, 145.95, 153.90 ppm;
ms: m/z (%) 360 (15) [Mþ], 265 (60), 231 (100), 216 (75),
202 (30), 144 (85), 94 (25). Anal. Calcd for C22H17ClN2O: C,
73.23; H, 4.71; N, 7.76%. Found: C, 73.16; H, 4.68; N,
7.72%.
EXPERIMENTAL
All commercially available chemicals and reagents were
used without further purification. Melting points were deter-
mined with an Electrothermal model 9100 apparatus and are
uncorrected. IR spectra were recorded on a Shimadzu 4300
spectrophotometer. The 1H and 13C NMR spectra were
recorded in DMSO-d6 on Bruker DRX-500 AVANCE spec-
trometers. Chemical shifts (d) are reported in ppm and are ref-
erenced 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-(X-substituted-
1-(4-Bromophenyl(pyridine-3-ylamino)methyl)naphthalene-
2-ol (2d). IR (potassium bromide): 3373, 3051, 2915, 1627,
1
1249, 806 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.53 (d, J
¼ 6.3 Hz, 1H, methine-H), 6.71 (d, J ¼ 6.3 Hz, 1H, NH),
7.02–8.12 (m, 14H, NPh-H, Ph-H, and Pyridine-H), 10.26 (s,
1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): d 52.93,
119.10, 119.25, 120.33, 123.35, 124.38, 124.60, 124.72,
127.10, 129.52, 129.67, 129.82, 130.41, 131.91, 132.96,
136.78, 138.28, 142.75, 145.29, 153.87 ppm; ms: m/z (%) 404
(15) [Mþ], 406 (15) [Mþ], 311 (80), 231 (100), 202 (80), 144
(25), 94 (50). Anal. Calcd for C22H17BrN2O: C, 65.18; H,
4.19; N, 6.91%. Found: C, 65.21; H, 4.11; N, 6.89%.
phenyl(pyridine-3-ylamino)methyl)naphthalene-2-ol
(2a–
1-(3-Bromophenyl(pyridine-3-ylamino)methyl)naphthalene-
2-ol (2e). IR (potassium bromide): 3394, 3053, 2923, 1625,
g). To a stirring suspension of 2-naphthol (1.44 g, 10 mmol)
in water (15 mL), the appropriate aromatic aldehyde (10
mmol) and 3-aminopyridine (10 mmol) was added. The reac-
tion mixture was stirred at 50ꢀC for the appropriate time (see
Table 1). Then water was decanted and the white precipitated
product was separated upon addition of ethanol (10 mL) to the
mixture with stirring, while cooling to 0–5ꢀC. The precipitate
was filtered, washed with cold EtOH, dried, and purified by
recrystallization from EtOH to give the colorless crystals of
2a–g.
1
1238, 817 cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.59 (d, J
¼ 6.3 Hz, 1H, methine-H), 6.75 (d, J ¼ 6.3 Hz, 1H, NH),
7.02–8.15 (m, 14H, NPh-H, Ph-H, and Pyridine-H), 10.32 (s,
1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): d 52.96,
119.10, 119.15, 119.25, 122.51, 123.39, 124.37, 126.67,
127.21, 129.55, 129.60, 130.13, 130.21, 130.48, 131.25,
131.90, 132.94, 136.78, 138.36, 145.16, 146.19, 153.94 ppm;
ms: m/z (%) 404 (100) [Mþ], 406 (100) [Mþ], 311 (10), 231
(20), 202 (8), 144 (15), 95 (25). Anal. Calcd for C22H17BrN2O:
C, 65.18; H, 4.19; N, 6.91%. Found: C, 65.14; H, 4.16; N,
6.97%.
1-(Phenyl(pyridine-3-ylamino)methyl)naphthalene-2-ol (2a).
IR (potassium bromide): 3394, 3068, 2900, 1625, 1240, 804
1
cmꢁ1; H NMR (500 MHz, DMSO-d6): d 6.55 (d, J ¼ 6.6 Hz,
1H, methine-H), 6.72 (d, J ¼ 6.6 Hz, 1H, NH), 7.00–8.15 (m,
15H, NPh-H, Ph-H, and Pyridine-H), 10.25 (s, 1H, OH) ppm;
1H NMR (500 MHz, DMSO-d6 þ D2O): d 6.57 (s, 1H,
methine-H), 7.01–8.09 (m, 15H, NPh-H, Ph-H, and Pyridine-
H) ppm; 13C NMR (125 MHz, DMSO-d6): d 53.39, 119.08,
119.17, 119.56, 123.26, 124.34, 124.94, 126.91, 127.32,
127.59, 129.06, 129.45, 129.70, 130.19, 133.08, 136.73,
1-(4-Nitrophenyl(pyridine-3-ylamino)methyl)naphthalene-2-
ol (2f). IR (potassium bromide): 3406, 3087, 2916, 1627,
1
1514, 1346, 1244, 827 cmꢁ1; H NMR (500 MHz, DMSO-d6):
d 6.68 (d, J ¼ 6.3 Hz, 1H, methine-H), 6.81 (d, J ¼ 6.3 Hz,
1H, NH), 7.06–8.19 (m, 14H, NPh-H, Ph-H, and Pyridine-H),
10.35 (s, 1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): d
53.29, 119.08, 119.11, 119.14, 119.37, 123.47, 124.28, 124.44,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

September 2009
Synthesis of Novel Naphth[1,2-f][1,4]oxazepine-3,4-dione Heterocycles
917
127.37, 128.69, 129.58, 129.64, 130.76, 132.92, 136.86,
138.53, 145.17, 147.01, 151.70, 153.93 ppm; ms: m/z (%) 371
(12) [Mþ], 260 (30), 231 (100), 202 (50), 144 (15), 94 (22).
Anal. Calcd for C22H17N3O3: C, 71.16; H, 4.58; N, 11.32%.
Found: C, 71.20; H, 4.57; N, 11.22%.
127.00, 128.17, 128.54, 129.20, 129.61, 129.64, 131.49,
131.76, 132.08, 134.33, 136.60, 137.40, 143.09, 147.41,
149.40, 149.43, 149.48, 149.90 ppm; ms: m/z (%) 415 (10)
[Mþ], 386 (50), 265 (90), 231 (100), 202 (50). Anal. Calcd
For C24H15ClN2O3: C, 69.48; H, 3.62; N, 6.75%. Found: C,
69.42; H, 3.59; N, 6.80%.
1-(3-Nitrophenyl(pyridine-3-ylamino)methyl)naphthalene-2-
ol (2g). IR (potassium bromide): 3390, 3078, 2925, 1622,
1-(4-Bromophenyl)-2-(pyridine-3-yl)-1,2-dihydronaphth[1,2-
f][1,4]oxazepine-3,4-dione (3d). Yield: 80%; mp: 225–227ꢀC;
1
1527, 1348, 1236, 804 cmꢁ1; H NMR (500 MHz, DMSO-d6):
IR (potassium bromide): 1720, 1637 cmꢁ1 1H NMR (500
;
d 6.71 (d, J ¼ 6.7 Hz, 1H, methine-H), 6.93 (d, J ¼ 6.7 Hz,
1H, NH), 7.10–8.23 (m, 14H, NPh-H, Ph-H, and Pyridine-H),
10.40 (s, 1H, OH) ppm; 13C NMR (125 MHz, DMSO-d6): d
53.01, 118.75, 119.21, 120.07, 122.09, 122.46, 123.49, 124.22,
124.71, 127.45, 129.59, 129.64, 130.60, 130.80, 132.91,
134.32, 136.07, 137.90, 145.28, 145.81, 148.71, 154.10 ppm;
ms: m/z (%) 371 (12) [Mþ], 276 (50), 260 (65), 231 (100),
202 (75), 144 (90), 94 (85). Anal. Calcd for C22H17N3O3: C,
71.16; H, 4.58; N, 11.32%. Found: C, 71.11; H, 4.50; N,
11.25%.
MHz, DMSO-d6): d 6.71 (s, 1H, methine-H), 7.25-8.54 (m,
14H, NPh-H, Ph-H, and Pyridine-H) ppm; 13C NMR (125
MHz, DMSO-d6): d 62.88, 115.36, 117.53, 122.77, 124.05,
124.88, 126.33, 128.45, 129.19, 129.60, 130.57, 131.48,
131.67, 132.95, 136.60, 137.47, 140.14, 147.30, 149.40,
149.41, 149.43, 149.92 ppm; ms: m/z (%) 458 (5)[Mþ], 460
(5) [Mþ], 430 (12), 432 (12), 309 (25), 311 (25), 231 (90),
202 (25), 167 (80), 149 (100). Anal. Calcd for C24H15BrN2O3:
C, 62.74; H, 3.26; N, 6.10%. Found: C, 62.70; H, 3.33; N,
6.14%.
General procedure for the synthesis of 1-(X-substituted-
phenyl)-2-(pyridin-3-yl)-1,2-dihydronaphth[1,2-f][1,4]oxaze-
pine-3,4-diones (3a–g). Oxalyl chloride (1.2 mmol) was added
dropwise with ice cooling to a stirring solution of 1-(X-substi-
tuted-phenyl(pyridine-3-ylamino)methyl)naphthalene-2-ol 2a–g
(1 mmol) in dry 1,2-dichloroethane (15 mL) containing pyri-
dine (2.4 mmol) under argon atmosphere. The mixture was
stirred for 30 min at 0–5ꢀC, then 30 min at room temperature,
and refluxed for an additional 45 min. The solvent was then
removed under reduce pressure to give a solid compound. It
was then triturated in saturated sodium bicarbonate solution
(15 mL), filtered, washed with distilled water, and dried. The
crude product was recrystallized from EtOH to give colorless
crystals of 3a–g.
1-(3-bromophenyl)-2-(pyridine-3-yl)-1,2-dihydronaphth[1,2-
f][1,4]oxazepine-3,4-dione (3e). Yield: 78%; mp: 220–222ꢀC;
IR (potassium bromide): 1724, 1639 cmꢁ1 1H NMR (500
;
MHz, DMSO-d6): d 6.73 (s, 1H, methine-H), 7.26–8.56 (m,
14H, NPh-H, Ph-H, and Pyridine-H) ppm; 13C NMR (125
MHz, DMSO-d6): d 62.78, 115.20, 117.56, 122.92, 124.02,
124.86, 126.39, 127.37, 128.55, 129.18, 129.63, 131.00,
131.49, 131.78, 132.34, 132.52, 136.61, 137.39, 143.28,
147.41, 149.41, 149.45, 149.48, 149.89 ppm; ms: m/z (%) 458
(5)[Mþ], 460 (5)[Mþ], 430 (12), 432 (12), 309 (50), 311 (50),
231 (90), 202 (50), 167 (40), 149 (100). Anal. Calcd for
C24H15BrN2O3: C, 62.74; H, 3.26; N, 6.10%. Found: C, 62.80;
H, 3.21; N, 6.02%.
1-(4-Nitrophenyl)-2-(pyridine-3-yl)-1,2-dihydronaphth[1,2-f]
[1,4]oxazepine-3,4-dione (3f). Yield: 78%; mp: 205–207ꢀC;
1-Phenyl-2-(pyridine-3-yl)-1,2-dihydronaphth[1,2-f][1,4]oxa-
zepine-3,4-dione (3a). Yield: 85%; mp: 232–234ꢀC; IR (potas-
IR (potassium bromide): 1720, 1633, 1519, 1348 cmꢁ1 1H
;
;
sium bromide): 1718, 1635 cmꢁ1 1H NMR (500 MHz,
NMR (500 MHz, DMSO-d6): d 6.92 (s, 1H, methine-H), 7.48–
8.55 (m, 14H, NPh-H, Ph-H, and Pyridine-H) ppm; 13C NMR
(125 MHz, DMSO-d6): d 62.59, 114.85, 117.61, 123.97,
124.93, 125.25, 126.43, 128.60, 129.15, 129.66, 129.83,
129.85, 131.50, 131.98, 136.64, 137.34, 147.50, 147.68,
148.30, 149.30, 149.57, 149.92 ppm; ms: m/z (%) 425 (6)
[Mþ], 397 (18), 279 (50), 260 (47), 231 (80), 202 (30), 167
(90), 149 (100). Anal. Calcd For C24H15N3O5: C, 67.76; H,
3.53; N, 9.88%. Found: C, 67.80; H, 3.52; N, 9.87%.
DMSO-d6): d 6.23 (s, 1H, methine-H), 7.22–8.62 (m, 15H,
NPh-H, Ph-H, and Pyridine-H) ppm; 13C NMR (125 MHz,
DMSO-d6): d 65.41, 114.75, 117.35, 122.69, 124.23, 125.86,
128.06, 128.17, 129.18, 129.42, 129.54, 129.73, 131.28,
131.47, 136.41, 137.54, 139.39, 147.53, 149.50, 149.48,
149.53, 150.00 ppm; ms: m/z (%) 380 (5) [Mþ], 352 (35), 231
(100), 202 (45). Anal. Calcd for C24H16N2O3: C, 75.79; H,
4.21; N, 7.37%. Found: C, 75.70; H, 4.25; N, 7.40%.
1-(4-Chlorophenyl)-2-(pyridine-3-yl)-1,2-dihydronaphth[1,2-f]
[1,4]oxazepine-3,4-dione (3b). Yield: 83%; mp: 245–246ꢀC; IR
1-(3-Nitrophenyl)-2-(pyridine-3-yl)-1,2-dihydronaphth[1,2-f]
[1,4]oxazepine-3,4-dione (3g). Yield: 80%; mp: 202–203ꢀC;
(potassium bromide): 1718, 1635 cmꢁ1 1H NMR (500 MHz,
;
IR (potassium bromide): 1725, 1638, 1524, 1349 cmꢁ1 1H
;
DMSO-d6): d 6.73 (s, 1H, methine-H), 7.32–8.55 (m, 14H,
NPh-H, Ph-H, and Pyridine-H) ppm; 13C NMR (125 MHz,
DMSO-d6): d 62.81, 115.42, 117.54, 124.06, 124.86, 126.33,
128.44, 129.20, 129.60, 130.03, 130.28, 131.48, 131.66,
131.66, 134.11, 136.61, 137.47, 139.75, 147.31, 149.41,
149.43, 149.94 ppm; ms: m/z (%) 415 (10) [Mþ], 386 (15),
279 (40), 231 (50), 202 (20), 167 (90), 149 (100). Anal. Calcd
For C24H15ClN2O3: C, 69.48; H, 3.62; N, 6.75%. Found: C,
69.51; H, 3.55; N, 6.70%.
NMR (500 MHz, DMSO-d6): d 6.95 (s, 1H, methine-H), 7.46–
8. (m, 14H, NPh-H, Ph-H, and Pyridine-H) ppm; 13C NMR
(125 MHz, DMSO-d6): d 62.49, 114.83, 117.60, 123.04,
123.99, 124.57, 124.88, 126.45, 128.65, 129.14, 129.20,
129.67, 131.50, 131.73, 132.02, 134.94, 136.84, 137.23,
142.63, 147.57, 148.91, 149.29, 149.59, 150.09 ppm; ms: m/z
(%) 425 (5) [Mþ], 397 (15), 279 (60), 260 (50), 231 (85), 202
(30), 167 (92), 149 (100). Anal. Calcd for C24H15N3O5: C,
67.76; H, 3.53; N, 9.88%. Found: C, 67.69; H, 3.50; N,
9.92%.
1-(3-Chlorophenyl)-2-(pyridine-3-yl)-1,2-dihydronaphth[1,2-f]
[1,4]oxazepine-3,4-dione (3c). Yield: 76%; mp: 222–223ꢀC; IR
(potassium bromide): 1724, 1639 cmꢁ1 1H NMR (500 MHz,
;
DMSO-d6): d 6.74 (s, 1H, methine-H), 7.28–8.56 (m, 14H,
NPh-H, Ph-H, and Pyridine-H) ppm; 13C NMR (125 MHz,
DMSO-d6): d 62.82, 115.22, 117.57, 124.03, 124.85, 126.38,
Acknowledgments. The authors wish to thank the Research
Council of the University of Tehran and Payame Noor University
of Qazvin for financial supports.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

918
M. Ghandi, A. Olyaei, and S. Raoufmoghaddam
Vol 46
[13] Heydenreich, M.; Koch, A.; Kold, S.; Szatmari, I.; Fulop,
F.; Kleinpeter, E. Tetrahedron 2006, 62, 11081.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet