Microwave-Assisted Rapid Synthesis of Novel 1,5-Benzodiazepine Derivatives as Potent Antimicrobial Agent

Article abstract of DOI:10.1002/jhet.1065

A new series of highly functionalized 1,5-benzodiazepine derivatives 5a-x have been synthesized from 3-[(1E)-N-(2-aminophenyl) ethanimidoyl]-4-hydroxyl- 2H-chromen-2-one 3a-c and pyrazole aldehyde 4a-h using catalytic amount of triflouro acetic acid under microwave irradiation. The main significant of the present procedure is shorter reaction time, easy work up procedure, and excellent yield with high purity. The structures of all the compounds were established on the basis of their IR, NMR, and mass spectral data and have been screened for their antimicrobial activity and antifungal activity.

Full text of DOI:10.1002/jhet.1065

February 2013
Microwave‐Assisted Rapid Synthesis of Novel
E73
1,5‐Benzodiazepine Derivatives as Potent Antimicrobial Agent
Shailesh Thakrar, Abhay Bavishi, Ashish Radadiya, Shrey Parekh,
Dhairya Bhavsar, Hardevsinh Vala, Nilay Pandya, and Anamik Shah
*
Department of Chemistry, Saurashtra University, Rajkot 360005, India
*
E-mail: anamik_shah@hotmail.com
Received February 23, 2011
DOI 10.1002/jhet.1065
Published online 21 February 2013 in Wiley Online Library (wileyonlinelibrary.com).
A new series of highly functionalized 1,5‐benzodiazepine derivatives 5a–x have been synthesized from 3‐
[(1E)‐N‐(2‐aminophenyl) ethanimidoyl]‐4‐hydroxyl‐2H‐chromen‐2‐one 3a–c and pyrazole aldehyde 4a–h using
catalytic amount of triflouro acetic acid under microwave irradiation. The main significant of the present procedure
is shorter reaction time, easy work up procedure, and excellent yield with high purity. The structures of all the
compounds were established on the basis of their IR, NMR, and mass spectral data and have been screened for
their antimicrobial activity and antifungal activity.
J. Heterocyclic Chem., 50, E73 (2013).
INTRODUCTION
Recently, pyrazoles containing aryl substituted emerged as
p38 Kinase inhibitors, antiparasitic activities [34]. Because of
their wide range of biological, industrial, and synthetic applica-
tions, the development of mild and efficient protocols continues
to be a challenging endeavor in synthetic organic chemistry.
These finding prompted us to synthesize pyrazole containing
1,5‐benzodiazepines functionalized with 4‐hydroxyl coumarin
for biological interest. We report here a method for the prepara-
tion of highly functionalized 1,5‐benzodiazepine derivatives us-
ing triflouro acetic acid as catalyst under microwave irradiation.
Benzodiazepines have recently received great impor-
tance because of their wide range of therapeutic and
pharmacological properties. These compounds are widely
used as anticonvulsant, antianxiety, analgesic, sedative,
antidepressive, hypnotic agents, and anti‐inflammatory
agents [1,2]. Moreover, benzodiazepine derivatives are
commercially used as dyes for acrylic fibers [3]. In the last
decade, the area of biological interest of 1,5‐benzodiazepines
has been extended to several diseases such as cancer, viral
infection, and cardiovascular disorders [4,5].
In addition, 1,5‐benzodiazepines are key intermediates for
the synthesis of various fused ring systems such as triazolo‐,
oxadiazolo‐, oxazino‐, or furan benzodiazepines [6–9].
Generally, these types of compounds are synthesized by the
condensation of o‐phenylenediamines with α, β‐unsaturated
carbonyl compounds [10], β‐haloketones, or ketones [11].
Because of their versatile applications, various methods for
the synthesis of benzodiazepines have been reported in the lit-
erature [12–31] (Fig. 1).
RESULTS AND DISCUSSION
In the first instance, 3‐acetyl 4‐hydroxy coumarin 1a–c
was synthesized by reported method [35]. Further, the reaction
of 3‐acetyl 4‐hydroxy coumarin 1a–c with o‐phenylene di-
amine 2 in ethanol for 8–10 h afforded 3a–c (Scheme 1). Then,
the condensation of newly synthesized 3a–c and 4a–h in the
presence of triflouro acetic acid under microwave irradiation
in methanol for 15–20 min afforded 5a–x (Scheme 2).)
Moreover, pyrazole framework containing compounds
are well known for its antibacterial, anti HIV, anticancer,
anti‐inflammatory, analgesic, and hypoglycaemic activities
[32]. Pyrazoles are used as insecticids and pesticids be-
cause of their herbicidal and fungicidal activity [33].
Indeed, the reaction of 4a with 3a in different solvents
likes methanol, ethanol, isopropanol, Chloroform, THF,
ethyl acetate, and DMF was observed using microwave ir-
radiation. Under the optimized conditions, we found that
the reaction proceeds well in polar solvents giving slight
© 2013 HeteroCorporation

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S. Thakrar, A. Bavishi, A. Radadiya, S. Parekh, D. Bhavsar, H. Vala, N. Pandya, and A. Shah
Vol 50
when compared with other solvents. In conclusion, a new
method developed for novel 1,5‐benzothiazepine derivatives,
which is rapid and high yielding. The antimicrobial activity of
these compounds was evaluated against various bacteria and
fungi. Most of the compounds showed a moderate degree
of antimicrobial activity. Compound 5g seems to be most
active among the whole data series because it has shown
potency to all the four strains, whereas compounds 5h, 5i,
5l, 5o, 5p, 5s, 5w, and 5x are moderately active molecules.
With this set of analogs, we are now in a position to investi-
gate the multiple biological activities of these compounds.
EXPERIMENTAL
All the melting points are uncorrected. Formation of the com-
pounds was routinely checked by TLC on silica gel‐G plates of
0.5‐mm thickness, and spots were located by iodine and UV.
All the reaction was carried out in Q‐Pro‐M microwave synthe-
sizer. The IR spectra were recorded on a Shimadzu FT‐IR‐8400
instrument using KBr pellet method. Mass spectra were recorded
on Shimadzu GC‐MS‐QP‐2010 model using Direct Injection
Figure 1. Biologically active benzodiazepine derivatives.
variations in reaction time and that methanol was the best
choice for this reaction with high yield. (Tables 1 and 2).
Antimicrobial and antifungal activities of compounds
5a–x. The newly synthesized benzodiazepine compounds
5a–x have been screened for antimicrobial activity against
Staphylococcus typhi, Staphylococcus pyogenus, and Vibrio
cholera and antifungal activity against Candida albicans by
Broth dialution method [36,37]. Ampicillin, chloramphenicol,
nystatin, and greseofulvin were used as standards for
comparison of antimicrobial and antifungal activity. The result
indicates that some of these compounds were active against
all the four organisms. The results of antimicrobial and
1
Probe technique. H‐NMR was determined in CDCl3/DMSO so-
lution on a Bruker Ac 400 MHz spectrometer. Elemental analysis
of the all the synthesized compounds were carried out on Elemental
Vario EL III Carlo Erba 1108 model, and the results are in agree-
ments with the structures assigned.
Synthesis of (E)‐3‐(1‐((2‐aminophenyl)imino)ethyl)‐
4‐hydroxy‐2H‐chromen‐2‐one (3a‐c). 3‐Acetyl‐4‐hydroxy
coumarin 1a–c (0.01 mol) and O‐phenylene diamine 2 (0.01
mol) were dissolved in 30 mL ethanol and refluxed the
content for 8–10 h. The reaction was monitored through TLC.
Solid separated out a to be filtered and washed with chilled
methanol, recrystallize it from mixture of methanol–DMF.
Purity of the compounds was checked through TLC using
ethyl acetate:hexane (6:4) system as the mobile phase.
General procedure for the synthesis of 3‐(2‐(1,3(substituted)‐
dipheyl‐1H‐pyrazol‐4‐yl)‐2,3‐dihydro‐1H‐benzo[b][1,4]diazepin‐
4‐yl)‐4‐hydroxy‐2H‐chromen‐2‐one (5a–x). 3‐[(1E)‐N‐(2‐
Aminophenyl) ethanimidoyl]‐4‐hydroxy‐2H‐chromen‐2‐one 3a–c
(0.01 mol) and substituted pyrazole aldehydes 4a–h (0.01 mol)
were dissolved in a methanol and subjected to Q‐Pro‐M microwave
synthesizer for appropriate time at 200 W (70°C) with catalytic
amount of triflouroacetic acid. During the reaction, the progress and
the completion of reaction were checked by silica gel‐G F254 thin
layer chromatography using ethyl acetate:hexane (3:2) as a mobile
phase. Pour the content into crushed ice. The solid separated out
antifungal activity are cited in Table 3.
Structure–activity relationship. SAR studies enlights that
1,5‐benxodiazepines can be optimized for the S. pyogenus
and also for S. typhi. Particularly, compound 5g can be
optimized for the broad spectrum of activity. Herein, -NO2
strong electron donating group induces the potency. Thus,
molecules having -NO2 group at 3 position shown more
potency. [Molecules (5l MIC = 69.8), (5w MIC = 62.5)].
Also, compounds having bulky group attached at 5th and
8th position of coumarin ring also favors the potency.
CONCLUSIONS
During the reaction procedure, we have observed that
the time taken by 5a in methanol is less and yield is high
Scheme 1. Synthesis of 3‐(2‐(1,3(substituted)‐dipheyl‐1H‐pyrazol‐4‐yl)‐2,3‐dihydro‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐2‐one (5a–x).
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Microwave-Assisted Rapid Synthesis of Novel 1,5-Benzodiazepine Derivatives
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Scheme 2. Synthesis of 3‐(2‐(1,3(substituted)‐dipheyl‐1H‐pyrazol‐4‐yl)‐2,3‐dihydro‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐2‐one (5a–x).
was filtered, washed, dried, and recrystallized it from methanol.
Spectral data for selected products 5a–x.
Table 1
Solvent effect on yield.
3‐(2‐(1,3‐Diphenyl‐1H‐pyrazol‐4‐yl)‐2,3‐dihydro‐1H‐benzo[b]
[1,4]dizepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐2‐one (5a). Melting
point 180–182°C; Yield: 94%; IR (cm−1): 3606, 3425, 3090, 3061,
2988, 2823, 1776, 1606, 1562, 1454, 1429, 1374, 1221, 766, 692,
Entry
5a
5a
5a
5a
5a
5a
5a
Solvent
Time
Yielda (%)
MeOH
EtOH
IPA
CH2Cl2
THF
9
11
9
12
14
12
16
94
92
89
85
89
87
82
1
702. H‐NMR (DMSO‐d6) δ ppm: 3.28–3.34(d, 2H), 4.45(s, 1H),
5.54–5.59(d, 1H), 6.91–6.93(d, 1H), 7.09–7.15(t, 1H), 7.21–7.27
(m, 5H), 7.31–7.34(t, 2H), 7.46–7.48(d, 2H), 7.52–7.58(t, 3H),
7.64–7.68(t, 1H), 7.76–7.78(d, 2H, J = 8.0 Hz), 8.03(s, 1H),
8.09–8.12(d, 1H), 15.76(s, 1H), MS: m/z = 524.18; Anal. Calcd. for
C33H24N4O3 C, 75.56; H, 4.61; N, 10.68; O, 9.15; Found: C,
75.46; H, 4.56; N, 10.68; O, 9.09(%).
EA
DMF
aIsolated yields after purification.
Table 2
Physical data.
Substitution
Time
(min)
Yielda
(%)
Entry
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
5p
5q
5r
5s
R1
R
MF
MP (°C)
H
H
H
H
H
H
H
H
H
C
33H24N4O3
180–182
204–206
226–228
208–210
196–198
188–190
210–212
178–180
186–188
168–170
194–196
206–208
178–180
166–168
218–220
208–210
178–180
212–214
202–204
182–184
176–178
218–220
192–194
188–190
9
8
11
7
94
89
88
82
89
88
85
86
85
91
88
86
88
92
86
87
89
92
84
89
87
92
86
89
4‐CH3
4‐NO2
2‐OH
2‐OCH3
4‐Cl
3‐NO2
4‐F
H
C34H26N4O3
C33H23N5O5
C33H24N4O4
C34H26N4O4
C33H23ClN4O3
C33H23N5O5
C33H23FN4O3
C34H26N4O3
C35H28N4O3
C34H25ClN4O3
C34H25N5O5
C34H26N4O4
C35H28N4O4
C34H25N5O5
C34H25FN4O3
C35H28N4O3
C36H30N4O3
C35H27ClN4O3
C35H27N5O5
C35H28N4O4
C36H30N4O4
C35H27N5O5
C35H27FN4O3
8
12
16
6
8
9
14
13
8
7
18
9
8‐CH3
8‐CH3
8‐CH3
8‐CH3
8‐CH3
8‐CH3
8‐CH3
8‐CH3
5,8‐di CH3
5,8‐di CH3
5,8‐di CH3
5,8‐di CH3
5,8‐di CH3
5,8‐di CH3
5,8‐di CH3
5,8‐di CH3
4‐CH3
4‐Cl
4‐NO2
2‐OH
2‐OCH3
3‐NO2
4‐F
H
4‐CH3
4‐Cl
4‐NO2
2‐OH
2‐OCH3
3‐NO2
4‐F
8
8
14
17
9
11
18
8
5t
5u
5v
5w
5x
aIsolated yields after purification.
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Vol 50
Table 3
C33H23N5O5: C, 69.59; H, 4.07; N, 12.30; O, 14.05, Found: C,
69.49; H, 4.04; N, 12.21; O, 14.01(%).
Antimicrobial and antifungal activities of compounds 5a–x.
3‐(‐2,3‐Dihydro‐2‐(3‐(2‐hydroxyphenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐
2‐one (5d). Melting point 208–210°C; Yield: 82%; IR (cm−1):
3601, 3523, 3383, 3221, 3115, 3051, 3014, 2945, 2879, 1786,
1674, 1604, 1566, 1483, 1462, 1415, 1346, 1242, 1205, 1159,
1126, 1085, 761,750, 682, 709. 1H‐NMR (DMSO‐d6) δ ppm:
3.28–3.34(d, 2H), 4.36(s, 1H), 5.33–5.36(s, 1H), 6.91–7.03
(m, 4H), 7.17–7.22(t, 2H), 7.24–7.30(m, 4H), 7.42–7.46
(t, 2H), 7.56–7.61(m, 2H), 7.71–7.73(d, 2H, J = 8.0 Hz),
8.00–8.02(d, 1H, J = 8.0 Hz), 8.31(s, 1H), 10.00(s, 1H), 15.60
(s, 1H), MS: m/z = 540.57; Anal. Calcd. for C33H24N4O4: C,
73.32; H, 4.48; N, 10.36; O, 11.84, Found: C, 73.24; H, 4.45;
N, 10.30; O, 11.79(%).
3‐(‐2,3‐Dihydro‐2‐(3‐(2‐methoxyphenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]dizepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐2‐one
(5e). Melting point 196–198°C; Yield: 89%; IR (cm−1): 3668, 3468,
3271, 3097, 3012, 2978, 2901, 1766, 1697, 1604, 1467, 1423, 1340,
1290, 1236, 1201, 1120, 1022, 765, 688, 708. 1H‐NMR (DMSO‐d6)
δ ppm: 2.85–3.00(q, 2H), 3.83(s, 3H), 4.49–4.52(s, 1H), 5.23–5.26
(d, 1H), 6.59–6.61(d, 1H, J = 8.0 Hz), 6.98–7.01(d, 2H),
7.02–7.10(m, 2H), 7.11–7.20(m, 4H), 7.26–7.31(m, 3H), 7.54–7.59
(t, 2H), 7.66–7.68(d, 2H, J = 8.0 Hz), 7.85(s, 1H), 15.59(s, 1H),
MS: m/z = 554.59; Anal. Calcd. for C34H26N4O4: C, 73.63; H,
4.73; N, 10.10; O, 11.54 Found: C, 73.43; H, 4.59; N, 10.03; O,
11.43(%).
3‐(‐2‐(3‐(4‐Chlorophenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)‐2,3‐
dihydro‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐
2‐one (5f). Melting point 188–190°C; Yield: 88%; IR (cm−1):
3568, 3448, 3071, 3037, 2988, 2891, 1746, 1687, 1624, 1453,
1440, 1236, 1286, 1201, 1120, 755, 688, 702. 1H‐NMR (DMSO‐d6)
δ ppm: 3.17–3.19(d, 2H), 4.49(s, 1H), 5.47(s, 1H), 6.82–6.85(t, 1H),
7.01–7.03(d, 1H), 7.25–7.27(d, 2H, J = 8.0 Hz ), 7.20–7.27(m, 5H),
7.45–7.49(t, 2H), 7.51–7.55(t, 1H), 7.64–7.66(d, 2H, J = 8.0 Hz),
7.78–7.82(d, 2H, J = 8.0 Hz), 8.19(s, 1H), 8.16–8.18(d, 1H, J = 8.0
Hz), 15.73 (s, 1H), MS: m/z = 559(M+), 562(M+2); Anal. Calcd. for
C33H23ClN4O3: C, 70.90; H, 4.15; Cl, 6.34; N, 10.02; O, 8.59
Found: C, 70.81; H, 4.07; Cl,6.30; N, 10.05; O, 8.46(%).
MIC value (μg/mL)
S.typhi Vi.cholerae S.pyogenus C.albicans
MTCC‐
98
MTCC‐
MTCC‐
MTCC‐
227
Entry
3906
442
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
5p
5q
5r
5s
5t
5u
5v
5w
5x
500
250
250
500
200
200
100
100
250
200
250
69.8
200
500
100
100
250
250
100
200
200
200
62.5
100
100
200
250
500
200
200
250
100
100
100
250
250
250
250
200
100
100
500
200
200
250
250
250
100
100
100
50
250
500
500
200
200
200
250
250
250
500
500
500
1000
250
250
500
250
200
500
250
500
500
250
200
100
50
500
250
250
1000
1000
500
250
500
250
250
500
1000
1000
1000
500
1000
>1000
500
500
200
200
200
1000
500
–
Ampicillin
Chloramphemicol 50
–
100
500
Nystatin
Greseofulvin
–
–
–
–
–
–
Bold values indicate that the compounds are active against the standard
drugs.
3‐(‐2,3‐Dihydro‐2‐(1‐phenyl‐3‐p‐tolyl‐1H‐pyrazol‐4‐yl)‐
1H‐benzo[b][1,4‐diazepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐2‐
one (5b). Melting point 204–206°C; Yield: 89%; IR (cm−1):
3576, 3556, 3525, 3190, 3161, 2978, 2833, 1766, 1676,
1606, 1562, 1492, 1464, 1419, 1354, 1211, 756, 681, 701.
1H‐NMR (DMSO‐d6) δ ppm: 2.39(s, 3H), 3.1–3.2(d, 2H),
4.5(s, 1H), 5.55(d, 1H), 6.90–6.93(d, 1H), 7.07–7.11
(t, 1H), 7.21–7.23(d, 2H, J = 8.0 Hz), 7.23–7.30(m, 5H),
7.40–7.45(t, 2H), 7.56–7.60(t, 1H), 7.66(d, 2H, J = 8.0
Hz), 7.72–7.75(d, 2H, J = 8.0 Hz), 8.00(s, 1H), 8.06–8.09
(d, 2H, J = 8.0 Hz), 15.70(s, 1H), MS = m/z = 538.20;
Anal. Calcd. for C34H26N4O3: C, 75.82; H, 4.87; N, 10.40;
O, 8.91; Found: C, 75.81; H, 4.80; N, 10.38; O, 8.81(%).
3‐(‐2,3‐Dihydro‐2‐(3‐(4‐nitrophenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐
2‐one (5c). Melting point 226–228°C; Yield: 88%; IR (cm−1):
3616, 3435, 3043, 3021, 2978, 2820, 1756, 1616, 1582, 1545,
3‐(‐2,3‐Dihydro‐2‐(3‐(3‐nitrophenyl)‐1‐phenyl‐1H‐pyrazol‐4‐
yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐2‐one
(5g). Melting point 210–212°C; Yield: 85%; IR (cm−1): 3623,
3323, 3115, 3041, 2935, 2869, 1776, 1675, 1634, 1560, 1482,
1425, 1326, 1232, 1215, 1169, 1136, 1075, 771, 760, 672, 719.
1H‐NMR (DMSO‐d6) δ ppm: 3.13–3.16(d, 2H), 4.52(s, 1H), 5.56
(s, 1H), 6.92–6.95(d, 1H), 7.17–7.20(t, 1H), 7.21–7.23(s, 1H),
7.25–7.27(d, 1H, J = 8.0 Hz), 7.30–7.33(d, 2H), 7.36–7.45
(m, 5H), 7.49–7.45(t, 2H), 7.56–7.60(t, 1H), 7.66–7.68(d, 2H,
J = 8.0 Hz), 8.03(s, 1H), 8.06–8.09(d, 1H, J = 8.0 Hz), 15.92
(s, 1H), MS: m/z = 569.57; Anal. Calcd. for C33H23N5O5: C,
69.59; H, 4.07; N, 12.30; O, 14.05 Found: C, 69.54; H, 4.06; N,
12.21; O, 14.02(%).
3‐(‐2‐(3‐(4‐Flourophenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)‐2,3‐dihylro‐
1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐2H‐chromen‐2‐one
(5h). Melting point 178–180°C; Yield: 86%; IR (cm−1): 3523,
3343, 3015, 3011, 2945, 2879, 1786, 1685, 1644, 1472, 1435,
1282, 1245, 1210, 1136, 761, 750, 692, 709. 1H‐NMR
(DMSO‐d6) δ ppm 3.21–3.25(d, 2H), 4.45(s, 1H), 5.45(s, 1H),
6.83–6.87(t, 1H), 7.10–7.13(d, 1H), 7.21–7.25(d, 2H, J = 8.0
Hz), 7.28–7.35(m, 5H), 7.45–7.49(t, 2H), 7.55–7.59(t, 1H),
7.66–7.68(d, 2H, J = 8.0 Hz), 7.76–7.78(d, 2H, J = 8.0 Hz),
8.18(s, 1H), 8.21–8.24(d, 1H, J = 8.0 Hz), 15.72(s, 1H), MS:
1
1444, 1419, 1364, 1211, 756, 691, 709. H‐NMR (DMSO‐d6) δ
ppm: 3.25–3.28(d, 2H), 4.47(s, 1H), 5.61(s, 1H), 6.91–6.94(d, 1H),
7.01–7.04(d, 1H), 7.15–7.17(d, 2H, J = 8.0 Hz), 7.22–7.31(m, 5H),
7.41–7.45(t, 2H), 7.53–7.58(t, 1H), 7.62–7.64(d, 2H, J = 8.0 Hz),
7.71–7.73(d, 2H, J = 8.0 Hz), 8.06(s, 1H), 8.12–8.14(d, 2H,
J = 8.0 Hz), 15.82(s, 1H), MS: m/z = 569.57; Anal. Calcd. for
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DOI 10.1002/jhet

February 2013
Microwave-Assisted Rapid Synthesis of Novel 1,5-Benzodiazepine Derivatives
as Potent Antimicrobial Agent
E77
m/z = 542, 544(M+2); Anal. Calcd. for C33H23FN4O3: C, 73.05;
H, 4.27; F, 3.50; N, 10.33; O, 8.85 Found: C, 73.00; H, 4.21; F,
3.42; N, 10.23; O, 8.75(%).
(s, 1H), 15.60(s, 1H), MS: m/z = 554.59; Anal. Calcd. for
C34H2604N4: C, 73.63; H, 4.73; N, 10.10; O, 11.54 Found:
C, 73.53; H, 4.61; N, 9.77; O, 11.41(%).
3‐(‐2,3‐Dihydro‐2‐(1,3‐diphenyl‐1H‐pyrazol‐4‐yl)‐1H‐benzo[b]
[1,4]diazepin‐4‐yl)‐4‐hydroxy‐8‐methyl‐2H‐chromen‐2‐one
(5i). Melting point 186–188°C; Yield: 85%; IR (cm−1):
3616, 3445, 3110, 3051, 2978, 2833, 1786, 1696, 1602,
1464, 1439, 1364, 1291, 1236, 1211, 1146, 765, 692, 719.
1H‐NMR (DMSO‐d6) δ ppm: 2.59(s, 3H), 3.17–3.22(d, 2H),
4.49(s, 1H), 5.50(s, 1H), 6.92–6.95(t, 1H), 7.07–7.11
(d, 1H), 7.23–7.25(d, 2H, J = 8.0 Hz), 7.33–7.40(m, 5H),
7.40–7.45(t, 2H), 7.66–7.68(d, 2H), 7.76(d, 2H, J = 8.0
Hz), 8.02(s, 1H), 8.06–8.09(d, 2H), 15.89(s, 1H), MS:
m/z = 538.60; Anal. Calcd. for C34H26N4O3: C,75.82; H,
4.87; N, 10.40; O, 8.91 Found: C, 72.83; H, 4.81;O, 8.89(%).
3‐(‐2,3‐Dihydro‐2‐(1‐phenyl‐3‐p‐tolyl‐1H‐pyrazol‐4‐yl)‐1H‐
benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐8‐mehyl‐2H‐chromen‐
2‐one (5j). Melting point 168–170°C; Yield: 91%; IR (cm−1):
3609, 3435, 3190, 3051, 2978, 2843, 1777, 1616, 1572, 1439,
3‐(‐2,3‐Dihydro‐2‐(3‐(2‐methoxyphenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]dizepin‐4‐yl)‐4‐hydroxy‐8‐methyl‐2H‐
chromen‐2‐one (5n). Melting point 166–168°C; Yield: 92%;
IR (cm−1): 3609, 3445, 3090, 3072, 2998, 2873, 1777, 1626,
1532, 1489, 1372, 1320, 1281, 1219, 1116, 766, 692, 719.
1H‐NMR (DMSO‐d6) δ ppm: 2.45(s, 3H), 2.85–3.00(q, 2H),
3.80(s, 3H), 4.41(s, 1H), 5.25–5.28(d, 1H), 6.58(d, 1H,
J = 8.0 Hz), 6.98–7.03(d, 2H), 7.17–7.24(m, 2H), 7.27–7.36
(m, 4H), 7.38–7.42(m, 3H), 7.48–7.53(t, 2H), 7.74–7.76(d,
2H, J = 8.0 Hz), 7.93(s, 1H), 8.13–8.16(d, 1H), 15.69(s, 1H),
MS: m/z = 568.62; Anal. Calcd. for C35H28N4O4: C, 73.93;
H, 4.96; N, 9.85; O, 11.25 Found: C, 73.83; H, 4.81; N, 9.67;
O, 11.15(%).
3‐(‐2,3‐Dihydro‐2‐(3‐(3‐nitrophenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐8‐methyl‐2H‐
chromen‐2‐one (5o). Melting point 218–220°C; Yield: 86%;
IR (cm−1): 3619, 3415, 3091, 3071, 2978, 2872, 1787, 1616,
1531, 1561, 1488, 1371, 1321, 1271, 1209, 1106, 776, 691,
709. 1H‐NMR (DMSO‐d6) δ ppm: 2.70(s, 3H), 3.31–3.34
(d, 2H), 4.45(s, 1H), 5.65(s, 1H), 6.92–6.95(d, 1H), 7.09–7.14
(t, 1H), 7.25(s, 1H), 7.29–7.31(d, 1H, J = 8.0 Hz), 7.39–7.41
(d, 2H), 7.44–7.50(m, 5H), 7.54–7.58(t, 2H), 7.61–7.64
(s, 2H), 8.05(s, 1H), 8.06–8.09(d, 1H, J = 8.0 Hz), 15.61
(s, 1H), MS: m/z = 583.59; Anal. Calcd. for C34H25N5O5: C,
69.97; H, 4.32; N, 12.00; O, 13.71 Found: C, 69.91; H, 4.31;
N, 10.77; O, 13.69(%).
1
1384, 1211, 1212, 1146, 756, 681, 701. H‐NMR (DMSO‐d6)
δ ppm: 2.29(s, 3H), 2.49(s, 3H), 3.21–3.26(d, 2H), 4.47
(s, 1H), 5.58(s, 1H), 6.92–6.95(t, 1H), 7.18–7.20(d, 1H),
7.22–7.24(d, 2H, J = 8.0 Hz ), 7.39–7.45(m, 5H), 7.55–7.59
(t, 2H), 7.69–7.71(d, 2H, J = 8.0 Hz), 7.81–7.83(d, 2H,
J = 8.0 Hz), 8.27(s, 1H), 8.16–8.89(d, 1H, J = 8.0 Hz), 15.79
(s, 1H), MS: m/z: 552.62; Anal. Calcd. for C35H28N4O3: C,
76.07; H, 5.11; N, 10.14; O, 8.69 Found: C, 76.03; H, 5.01;
N, 10.07; O, 8.60(%).
3‐(‐2‐(3‐(4‐Chlorophenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)‐2,3‐dihydro‐
1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐8‐methyl‐2H‐chromen‐
2‐one (5k). Melting point 194–196°C; Yield: 88%; IR (cm−1):
3599, 3445, 3090, 3052, 2988, 2853, 1767, 1606, 1562, 1449,
3‐(‐2‐(3‐(4‐Flourophenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)‐2,3‐
dihylro‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐8‐methyl‐
2H‐chromen‐2‐one (5p). Melting point 208–210°C; Yield:
87%; IR (cm−1): 3589, 3455, 3098, 3082, 2988, 2883, 1778,
1636, 1522, 1479, 1382, 1321, 1282, 1209, 1110, 767, 691,
709. 1H‐NMR (DMSO‐d6) δ ppm: 2.59(s, 3H), 3.19–3.23
(d, 2H), 4.51(s, 1H), 5.59(s, 1H), 6.79–6.82(t, 1H),
7.10–7.13(d, 2H), 7.26–7.34(m, 5H), 7.45–7.49(t, 2H), 7.70–7.72
(d, 2H, J = 8.0 Hz), 7.80–7.82(d, 2H, J = 8.0 Hz), 8.01(s, 1H),
8.26–8.28(d, 1H, J = 8.0 Hz), 15.71(s, 1H), MS: m/z = 556, 558
(M+2); Anal. Calcd. for C34H25FN4O3: C, 73.37; H, 4.53; F, 3.41;
N, 10.07; O, 8.62 Found: C, 73.31; H, 4.51; F, 3.37; O, 10.01(%).
3‐(‐2,3‐Dihydro‐2‐(1,3‐diphenyl‐1H‐pyrazol‐4‐yl)‐1H‐benzo
[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐5,8‐dimethyl‐2H‐chromen‐2‐one
(5q). Melting point 178–180°C; Yield: 89%; IR (cm−1): 3601,
3435, 3080, 3062, 2988, 2883, 1776, 1636, 1542, 1479, 1382,
1
1374, 1221, 1201, 1126, 776, 689, 703. H‐NMR (DMSO‐d6) δ
ppm: 2.39 (s, 3H), 3.18–3.22(d, 2H), 4.39(s, 1H), 5.59(s, 1H),
6.91–6.94(d, 1H), 7.04–7.10(d, 1H), 7.21–7.23(d, 2H, J = 8.0
Hz), 7.23–7.30(m, 5H), 7.40–7.45(t, 2H), 7.66(d, 2H, J = 8.0 Hz),
7.72–7.75(d, 2H, J = 8.0 Hz), 8.21 (s, 1H), 8.02–8.04(d, 1H,
J = 8.0 Hz), 15.77(s, 1H), MS: m/z = 573, 575(M+2); Anal. Calcd.
for C34H25ClN4O3: C, 71.26; H, 4.40; Cl, 6.19; N, 9.78; O, 8.38
Found: C, 71.23; H, 4.31; Cl, 6.77; O, 8.31(%).
3‐(‐2,3‐Dihydro‐2‐(3‐(4‐nitrophenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐8‐methyl‐2H‐
chromen‐2‐one (5l). Melting point 206–208°C; Yield: 86%; IR
(cm−1): 3589, 3435, 3190, 3062, 2998, 2863, 1787, 1616, 1542,
1
1560, 1469, 1382, 1221, 1212, 1146, 766, 692, 701. H‐NMR
1
(DMSO‐d6) δ ppm: 2.41(s, 3H), 3.21–3.24(d, 2H), 4.45
(s, 1H), 5.52(s, 1H), 6.91–6.93(d, 1H), 7.01–7.05(t, 1H),
7.20–7.22(d, 2H, J = 8.0 Hz), 7.29–7.38(m, 5H), 7.41–7.45
(t, 2H), 7.68–7.70(d, 2H, J = 8.0 Hz), 7.82–7.84(d, 2H,
J = 8.0 Hz), 8.10(s, 1H), 8.12–8.14(d, 1H, J = 8.0 Hz), 15.61
(s, 1H), MS: m/z = 583.59; Anal. Calcd. for C34H25N5O5: C,
69.97; H, 4.32; N, 12.00; O, 13.71 Found: C, 69.83; H, 4.31;
N, 11.77; O, 13.69(%).
3‐(‐2,3‐Dihydro‐2‐(3‐(2‐hydroxyphenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐8‐methyl‐2H‐
chromen‐2‐one (5m). Melting point 178–180°C; Yield: 88%;
IR (cm−1): 3609, 3445, 3090, 3072, 2998, 2873, 1777, 1626,
1532, 1489, 1372, 1320, 1281, 1219, 1116, 766, 692, 719.
1H‐NMR (DMSO‐d6) δ ppm: 2.33(s, 3H), 3.28–3.34(d, 2H),
4.36(s, 1H), 5.33–5.36(s, 1H), 6.91–7.03(m, 4H), 7.17–7.22
(t, 2H), 7.24–7.30(m, 4H), 7.42–7.46(t, 2H), 7.56–7.61
(m, 2H), 7.71–7.73(d, 2H, J = 8.0 Hz), 8.31(s, 1H), 10.00
1321, 1271, 1219, 1117, 767, 691, 709. H‐NMR (DMSO‐d6) δ
ppm: 2.31(s, 6H), 3.19–3.22(d, 2H), 4.54(s, 1H), 5.51(s, 1H),
6.92–6.95 (d, 1H), 7.17–7.20(t, 1H), 7.21–7.23(d, 2H, J = 8.0
Hz), 7.23–7.30(m, 5H), 7.40–7.45(t, 2H), 7.56–7.60(t, 3H), 7.66
(d, 2H, J = 8.0 Hz), 8.09(s, 1H), 15.21(s, 1H), MS: m/z = 552.62;
Anal. Calcd. for C35H28N4O3: C, 76.07; H, 5.11; N, 10.14; O,
8.69 Found: C, 76.05; H, 5.01; N, 10.07; O, 8.58(%).
3‐(‐2,3‐Dihydro‐2‐(1‐phenyl‐3‐p‐tolyl‐1H‐pyrazol‐4‐yl)‐1H‐
benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐5,8‐dimethyl‐2H‐chromen‐
2‐one (5r). Melting point 212–214°C; Yield: 92%; IR (cm−1):
3619, 3455, 3091, 3082, 2997, 2871, 1767, 1616, 1542, 1499,
1371, 1310, 1271, 1218, 1106, 776, 682, 709. 1H‐NMR
(DMSO‐d6) δ ppm: 2.19 (s, 6H), 2.95(s, 3H), 3.25–3.26(d, 2H),
4.47(s, 1H), 5.67(s, 1H), 6.86–6.91(t, 1H), 7.08–7.12(d, 1H),
7.23–7.25(d, 2H, J = 8.0 Hz), 7.27–7.33(m, 5H), 7.41–7.46
(t, 2H), 7.70–7.72(d, 2H, J = 8.0 Hz), 7.79–7.81(d, 2H, J = 8.0
Hz), 8.19(s, 1H), 15.60(s, 1H), MS: m/z = 566.65; Anal. Calcd.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

E78
S. Thakrar, A. Bavishi, A. Radadiya, S. Parekh, D. Bhavsar, H. Vala, N. Pandya, and A. Shah
Vol 50
for C36H30N4O3: C,76.31; H, 5.34; N, 9.89; O, 8.47 Found: C,
76.23; H, 5.31; N, 9.77; O, 8.44(%).
3‐(‐2‐(3‐(4‐Flourophenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)‐2,3‐
dihylro‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐5,8‐dimethyl‐
2H‐chromen‐2‐one (5x). Melting point 188–190°C; Yield: 89%;
IR (cm−1): 3612, 3445, 3191, 3082, 2998, 2861, 1786, 1626,
3‐(‐2‐(3‐(4‐Chlorophenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)‐2,3‐
dihydro‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐5,8‐dimethyl‐
2H‐chromen‐2‐one (5s). Melting point 202–204°C; Yield: 84%;
IR (cm−1): 3639, 3455, 3099, 3071, 2988, 2883, 1778, 1616,
1542, 1499, 1382, 1321, 1271, 1229, 1106, 776, 682, 729.
1H‐NMR (DMSO‐d6) δ ppm : 2.29 (s, 6H), 3.20–3.23(d, 2H),
4.40(s, 1H), 5.77(s, 1H), 6.87–6.91(t, 1H), 7.18–7.21(d, 1H),
7.33–7.35(d, 2H, J = 8.0 Hz), 7.41–7.49(m, 5H), 7.51–7.56
(t, 2H), 7.75–7.77(d, 2H, J = 8.0 Hz), 7.91–7.93(d, 2H, J =
8.0 Hz), 8.29(s, 1H), 15.94(s, 1H), MS: m/z = 587, 589(M+2);
Anal. Calcd. for C35H27ClN4O3: C, 71.61; H, 4.64; Cl, 6.04;
N, 9.54; O, 8.18 Found: C, 71.53; H, 4.51; Cl, 6.01; N, 9.51;
O, 8.17(%).
3‐(‐2,3‐Dihydro‐2‐(3‐(4‐nitrophenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐5,8‐dimethyl‐
2H‐chromen‐2‐one (5t). Melting point 182–184°C; Yield:
89%; IR (cm−1): 602, 3435, 3190, 3072, 2988, 2863, 1776,
1636, 1531, 1570, 1479, 1378, 1320, 1209, 769, 719.
1H‐NMR (DMSO‐d6) δ ppm: 2.71(s, 6H), 3.12–3.15(d, 2H),
4.41(s, 1H), 5.45(s, 1H), 6.81–6.84(t, 1H), 7.09–7.11(d, 1H),
7.22–7.24(d, 2H, J = 8.0 Hz), 7.29–7.35(m, 5H), 7.57–7.60
(t, 2H), 7.60–7.62(d, 2H, J = 8.0 Hz), 7.73–7.75(d, 2H, J = 8.0
Hz), 8.31(s, 1H), 15.48(s, 1H), MS: m/z = 597.62; Anal. Calcd. for
C35H27N5O5: C, 70.34; H, 4.55; N, 11.72; O,1 3.39 Found: C,
70.33; H, 4.51; N, 11.67; O, 13.26(%).
1
1521, 1478, 1388, 1321, 1201, 768, 718. H‐NMR (DMSO‐d6)
δ ppm: 2.79(s, 6H), 3.15–3.17(d, 2H), 4.49(s, 1H), 5.55(s, 1H),
6.82–6.86(t, 1H), 7.10–7.13(d, 1H), 7.42–7.44(d, 2H, J = 8.0
Hz), 7.49–7.59(m, 5H), 7.67–7.73(t, 2H), 7.80–7.82(d, 2H,
J = 8.0 Hz), 7.93–7.95(d, 2H, J = 8.0 Hz), 8.36(s, 1H), 15.58
(s, 1H), MS: m/z
=
570, 572(M+2); Anal. Calcd. for
C35H27FN4O3: C, 73.67; H, 4.77; F, 3.33; N, 9.82; O, 8.41
Found: C, 73.65; H, 4.59; F, 3.27; N, 9.79; O, 8.32(%).
Acknowledgments. The authors are thankful to FIST‐DST and
SAP‐UGC for their generous financial and instrumentation
support. Special thanks are due to “National Facility for Drug
Discovery through New Chemical Entities (NCEs) Development
and Instrumentation Support to Small Manufacturing Pharma
Enterprises” Programme under Drug and Pharma Research
Support (DPRS) jointly funded by Department of Science and
Technology, New Delhi, Government of Gujarat Industries
Commissionerate and Saurashtra University, Rajkot.
REFERENCES AND NOTES
[1] (a) Schutz, H. Benzodiazepines; Springer: Heidelberg, 1982;
(b) Landquist, J. K. In Comprehensive Heterocyclic Chemistry; Katritzky,
A. R., Rees, C. W., Eds.; Pergamon: Oxford, 1984; Vol. 1, pp 66– 170; (c)
Fryer, R. I. In Comprehensive Heterocyclic Chemistry; Taylor, E. C., Ed.;
Wiley: New York, 1991, Chapter 2, p 50; (d) Randall, L. O.; Kappel, B. In
Benzodiazepines; Garattini, S., Musini, E., Randall, L. O., Eds.; Raven
Press: New York, 1973, p 27.
[2] De Baun, J. R.; Pallos, F. M.; Baker, D. R. U.S. Pat.
3,978,227, 1976; Chem Abstr 1977, 86, 5498d.
[3] Harris, R. C.; Straley, J. M.; U.S. Patent 1968, 1,537,757;
Chem. Abstr. 1970, 73, 100054w.
[4] Merluzzi, V.; Hargrave, K. D.; Labadia, M.; Grozinger, K.; Skoog,
M.; Wu, J. C.; Shih, C.‐K.; Eckner, K.; Hattox, S.; Adams, J.; Rosenthal, A. S.;
Faanes, R.; Eckner, R. J.; Koup, R. A.; Sullivan, J. L. Science 1990, 250, 1411.
[5] Di Braccio, M.; Grossi, G.; Romoa, G.; Vargiu, L.; Mura, M.;
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Phosphorus Sulfur Silicon Relat Elem 2007, 182, 711.
[7] Nagaraja, G. K.; Vaidya, V. P.; Rai, K. S.; Mahadevan, K. M.
Phosphorus Sulfur Silicon Relat Elem 2006, 181, 2797.
[8] Nabih, K.; Baouid, A.; Hasnaoui, A.; Kenz, A. Synth Commun
2004, 34, 3565.
[9] Reddy, K. V.; Rao, P. S.; Ashok, D. Synth Commun 2000, 30, 1825.
[10] Stahlhofen, P.; Ried, W. Chem Ber 1957, 90, 815.
[11] Ried, W.; Torinus, E. Chem Ber 1959, 92, 2902.
[12] Herbert, J. A. L.; Suschitzky, H. J Chem Soc Perkin Trans
1974, 1, 2657.
3‐(‐2,3‐Dihydro‐2‐(3‐(2‐hydroxyphenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐5,8‐dimethyl‐2H‐
chromen‐2‐one (5u). Melting point 176–178°C; Yield: 87%; IR
(cm−1): 3612, 3455, 3191, 3032, 2998, 2861, 1786, 1646, 1541,
1
1479, 1378, 1321, 1219, 759, 709. H‐NMR (DMSO‐d6) δ ppm:
2.63(s, 6H), 3.38–3.41(d, 2H), 4.56(s, 1H), 5.23(s, 1H), 6.92–7.02
(m, 4H), 7.27–7.32 (t, 1H), 7.34–7.39(m, 4H), 7.52–7.56(t, 2H),
7.66 ‐7.76(m, 2H), 7.81–7.83(d, 2H, J = 8.0 Hz), 8.41(s, 1H),
10.50(s, 1H), 15.69(s, 1H), MS: m/z = 568.62; Anal. Calcd. for
C35H28N4O4: C,73.93; H, 4.96; N, 9.85; O, 11.25 Found: C,
73.83; H, 9.81; N, 9.77; O, 11.24(%).
3‐(‐2,3‐Dihydro‐2‐(3‐(2‐methoxyphenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]dizepin‐4‐yl)‐4‐hydroxy‐5,8‐dimethyl‐2H‐
chromen‐2‐one (5v). Melting point 218–220°C; Yield: 92%; IR
(cm−1): 3612, 3455, 3110, 3012, 2981, 2861, 1778, 1632, 1533,
1
1478, 1379, 1320, 1208, 768, 718. H‐NMR (DMSO‐d6) δ ppm:
2.12(s, 6H), 2.39(s, 3H), 3.12–3.162(d, 2H), 4.59(s, 1H), 5.35
(s, 1H), 6.59–6.61(d, 1H, J = 8.0 Hz), 6.91–9.95(d, 2H),
7.06–7.15(m, 2H), 7.17–7.26(m, 4H), 7.36–7.41(m, 3H),
7.49–7.53(t, 2H), 7.64–7.66(d, 2H, J = 8.0 Hz), 7.83(s, 1H),
8.03–8.05(d, 1H), 16.21(s, 1H), MS: m/z = 582.65; Anal. Calcd.
for C36H30N4O4: C, 74.21; H, 5.19; N, 9.62; O, 10.98 Found: C,
74.13; H, 5.11; N, 9.57; O, 10.91(%).
3‐(‐2,3‐Dihydro‐2‐(3‐(3‐nitrophenyl)‐1‐phenyl‐1H‐pyrazol‐
4‐yl)‐1H‐benzo[b][1,4]diazepin‐4‐yl)‐4‐hydroxy‐5,8‐dimethyl‐
2H‐chromen‐2‐one (5w). Melting point 192–194°C; Yield:
86%; IR (cm−1): 3582, 3445, 3120, 3071, 2998, 2863, 1776,
1636, 1531, 1570, 1479, 1378, 1320, 1209, 769, 719. 1H‐NMR
(DMSO‐d6) δ ppm: 2.70(s, 6H), 3.13–3.24(d, 2H), 4.35
(s, 1H), 5.55(s, 1H), 6.82–6.85(d, 1H), 7.01–7.04(t, 1H), 7.15
(s, 1H), 7.19–7.21(d, 1H, J = 8.0 Hz), 7.29–7.31(d, 2H),
7.54–7.60(m, 5H), 7.64–7.68(t, 2H), 7.71–7.64(d, 2H), 8.05
(s, 1H), 15.61(s, 1H), MS: m/z = 597.62; Anal. Calcd. for
C35H27N5O5: C, 70.34; H, 4.55; N, 11.72; O, 13.39 Found: C,
70.23; H, 4.51; N, 11.67; O, 13.31(%).
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