666 JOURNAL OF CHEMICAL RESEARCH 2014
Single-crystal x-ray crystallography
6′‑H), 8.92 (s, 1H, 5‑NH). IR (KBr) υ: 3318 br, 1604 m, 1511 s, 1386 m,
752 m, 700 m. Anal. calcd for C25H21ClN2O: C, 74.90; H, 5.28; N, 6.99;
found: C, 74.69; H, 5.04; N, 6.85%. MS (ESI) m/z: 401.2 (M+1).
Crystallographic data of 3a were collected using a Bruker SMART
APEX II CCD‑based diffractometer with graphite‑monochromatic
MoKα radiation (λ=0.71073 Å) at 291(2)K. Data reductions and
absorption corrections were performed using SAINT and SADABS
software packages,21 respectively. The structure was determined
using the SHELXL‑97 software package.22 Non‑hydrogen atoms were
refined anisotropically using the full‑matrix least‑squares method on
F2. All hydrogen atoms were placed at calculated positions and refined
riding on the parent atoms. Crystallographic data for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication CCDC No.1008694. The
crystallographic data of 3a are shown in Table 1.
1
3b‑2: Yield 36%; m.p. 222–224 °C. H NMR (DMSO‑d6, 500 MHz)
δ 2.42 (m, 1H, 2a‑H), 2.69 (m, 1H, 2b‑H), 2.87 (m, 1H, 4a‑H), 3.01
(m, 1H, 4b‑H), 3.39 (m, 1H, 3‑H), 5.77 (d, 1H, J=6.0 Hz, 11‑H), 6.31
(d, 1H, J=6.0 Hz, 10‑NH), 6.59–6.91 (m, 11H, PhH, 2′‑H, 6′‑H), 7.12
(m, 2H, 3′‑H, 5′‑H); 8.87 (s, 1H, 5‑NH). IR (KBr) υ: 3318 br, 1604 m,
1511 s, 1386 m, 752 m, 700 m. Anal. calcd for C25H21ClN2O: C, 74.90;
H, 5.28; N, 6.99; found: C, 74.65; H, 5.11; N, 6.89%. MS (ESI) m/z:
401.2 (M+1).
3-Phenyl-11-(4-methoxyphenyl)-2,3,4,5,10,11-hexahydro-1H-
dibenzo[b,e][1,4]diazepin-1-one (3c)
3c‑1: Yield 35%; m.p. 212–214 °C. 1H NMR (DMSO‑d6, 500 MHz) δ
2.53 (m, 2H, 2‑H), 2.91 (m, 1H, 4a‑H), 3.06 (m, 1H, 4b‑H), 3.45 (m,
1H, 3‑H), 3.62 (s, 3H, 4′‑OCH3), 5.64 (d, 1H, J=6.0 Hz, 11‑H), 6.16
(d, 1H, J=6.0 Hz, 10‑NH), 6.88–7.35 (m, 13H, PhH, 2′‑H, 3′‑H, 5′‑H,
6′‑H), 8.82 (s, 1H, 5‑NH); IR (KBr) υ: 3316 br, 1597 m, 1389 s, 1290 m,
770 m. Anal. calcd for C26H24N2O2: C, 78.76; H, 6.10; N, 7.07; found: C,
78.57; H, 5.83; N, 6.88%. MS (ESI) m/z: 397.2 (M+1).
5-((2-Aminophenyl)amino)-1,6-dihydro-[1,1′-biphenyl]-3(2H)-one
(2): Yield 92%; m.p. 208–210 °C. H NMR (DMSO‑d6, 500 MHz)
1
δ 2.26 (m, 1H, 4a‑H), 2.53 (m, 1H, 4b‑H), 2.66 (m, 1H, 6a‑H), 2.85
(m, 1H, 6b‑H), 4.72 (s, 1H, 2‑H), 4.92 (br, 2H, 14‑NH), 6.57 (m, 1H,
5‑H), 6.76–7.35 (m, 9H, PhH), 8.35 (s, 1H, 7‑NH). IR (KBr) υ: 3306 br,
1638 s, 1176 m, 1108 m, 738 m. Anal. calcd for C18H18N2O: C, 77.67; H,
6.52; N, 10.06; found: C, 77.32; H, 6.45; N, 9.84%. MS (ESI) m/z: 279.2
(M+1).
1
3c‑2: Yield 28%; m.p. 212–214 °C. H NMR (DMSO‑d6, 500 MHz)
3-Phenyl-11-(2-chlorophenyl)-2,3,4,5,10,11-hexahydro-1H-
dibenzo[b,e][1,4]diazepin-1-one (3a): Yield 65%; m.p. 136–138 °C.
1H NMR (DMSO‑d6, 500 MHz) δ 2.50 (m, 2H, 2‑H), 2.95 (m. 1H,
4a‑H), 3.13 (m, 1H, 4b‑H), 3.45 (m, 1H, 3‑H), 5.60 (d, 1H, J=6.0 Hz,
11‑H), 5.96 (d, 1H, J=6.0 Hz, 10‑NH), 6.48–6.64 (m, 4H, PhH), 9.10
(s, 1H, 5‑NH); 6.88–7.38 (m, 9H, PhH, 3′‑H, 4′‑H, 5′‑H, 6′‑H); IR (KBr)
υ: 3325 br, 1602 m, 1529 s, 1386 m, 754 m, 700 m. Anal. calcd for
C25H21ClN2O: C, 74.90; H, 5.28; N, 6.99; found: C, 74.75; H, 5.07; N,
6.95%. MS (ESI) m/z: 401.2 (M+1).
δ 2.42 (m, 1H, 2a‑H), 2.68 (m, 1H, 2b‑H), 2.87 (m, 1H, 4a‑H), 2.99
(m, 1H, 4b‑H), 3.38 (m, 1H, 3‑H), 3.64 (s, 3H, 4′‑OCH3), 5.74 (d, 1H,
J=5.5 Hz, 11‑H), 6.22 (d, 1H, J=6.5 Hz, 10‑NH), 6.58–6.69 (m,
11H, PhH, 2′‑H, 6′‑H), 7.09 (d, 2H, J=8.5 Hz, 3′‑H, 5′‑H), 8.78 (s, 1H,
5‑NH). IR (KBr) υ: 3316 br, 1597 m, 1389 s, 1290 m, 770 m. Anal.
calcd for C26H24N2O2: C, 78.76; H, 6.10; N, 7.07; found: C, 78.53; H,
5.86; N, 6.93%. MS (ESI) m/z: 397.2 (M+1).
3-Phenyl-11-(3,4-dimethoxyphenyl)-2,3,4,5,10,11-hexahydro-1H-
dibenzo[b,e][1,4]diazepin-1-one (3d): Yield 61%; m.p. 134–136 °C.
1H NMR (DMSO‑d6, 500 MHz) δ 2.66 (m, 2H, 2‑H), 2.99 (m, 1H,
4a‑H), 3.64 (m, 6H, 3′‑OCH3, 4′‑OCH3), 3.86 (m, 1H, 4b‑H), 3.86
(m, 1H, 3‑H), 5.73 (d, 1H, J=6.0 Hz, 11‑H), 6.23 (d, 1H, J=6.0 Hz,
10‑NH), 6.59–7.35 (m, 12H, PhH, 2′‑H, 5′‑H, 6′‑H), 8.77 (s, 1H, 5‑NH).
IR (KBr) υ: 3332 m, 2935 m, 1592 m, 1533 s, 1384 m, 1267 m, 757 m.
Anal. calcd for C27H26N2O3: C, 76.03; H, 6.14; N, 6.57; found: C, 75.87;
H, 5.80; N, 6.43%. MS (ESI) m/z: 427.1 (M+1).
3-Phenyl-11-(4-chlorophenyl)-2,3,4,5,10,11-hexahydro-1H-
dibenzo[b,e][1,4]diazepin-1-one (3b)
1
3b‑1: Yield 40%; m.p. 222–224 °C. H NMR (DMSO‑d6, 500 MHz)
δ 2.46 (m, 1H, 2a‑H), 2.60 (m, 1H, 2b‑H), 2.91 (m, 1H, 4a‑H), 3.09
(m, 1H, 4b‑H), 3.46 (m, 1H, 3‑H), 5.67 (d, 1H, J=6.0 Hz, 11‑H), 6.26
(d, 1H, J=6.0 Hz, 10‑NH), 7.04–7.39 (m, 13H, PhH, 2′‑H, 3′‑H, 5′‑H,
3-Phenyl-11-(naphthalen-1-yl)-2,3,4,5,10,11-hexahydro-1H-
dibenzo[b,e][1,4]diazepin-1-one (3e): Yield 80%; m.p. 166–168 °C.
1H NMR (DMSO‑d6, 500 MHz) δ 2.50 (m, 2H, 2‑H), 2.98 (m, 1H,
4a‑H), 3.17 (m, 1H, 4b‑H), 3.49 (m, 1H, 3‑H), 5.90 (d, 1H, J=6.5 Hz,
11‑H), 6.06 (d, 1H, J=8.0 Hz, 10‑NH), 6.46–6.78 (m, 4H, PhH),
7.04–8.55 (m, 12H, PhH+Naph–H), 9.01 (s, 1H, 5‑NH). IR (KBr) υ:
3329 m, 3025 m, 1598 m, 1390 s, 1290 m, 775 m, 700 m. Anal. calcd
for C29H24N2O: C, 83.63; H, 5.81; N, 6.73; found: C, 83.52; H, 5.65; N,
6.63%. MS (ESI) m/z: 417.1 (M+1).
Table 1 Crystallographic data for compound 3a
Identification
Empirical formula
Formula weight
Temperature/K
Wavelength/Å
3a
C25H23ClN2O2
418.90
291(2)
0.71073
Crystal system, space group
Unit cell dimensions
Monoclinic, P21/c
a=14.3192(17) Å, α=90°
b=7.9273(9)Å, β=97.831(2) °
c=18.744(2) Å, γ=90°
2107.8(4)
3,11-Diphenyl-2,3,4,5,10,11-hexahydro-1H-dibenzo[b,e][1,4]
diazepin-1-one (3f)
1
3f‑1: Yield 50%; m.p. 206–208 °C. H NMR (DMSO‑d6, 500 MHz)
δ 2.46 (m, 1H, 2a‑H), 2.60 (m, 1H, 2b‑H), 2.89 (m, 1H, 4a‑H), 3.09 (m,
1H, 4b‑H), 3.46 (m, 1H, 3‑H), 5.70 (d, 1H, J=6.0 Hz, 11‑H), 6.24 (d,
1H, J=6.0 Hz, 10‑NH), 6.89–7.36 (m, 14H, PhH), 8.88 (s, 1H, 5‑NH).
IR (KBr) υ: 3295 m, 1594 m, 1529 s, 1388 m, 754 m, 698 m. Anal. calcd
for C25H22N2O: C, 81.94; H, 6.05; N, 7.64; found: C, 81.80; H, 5.78; N,
7.56%. MS (ESI) m/z: 367.2 (M+1).
Volume/Å3
Z
4
Calculated density/g cm–3
Absorption coefficient/ mm–1
F(000)
1.320
0.206
880
1
3f‑2: Yield 25%; m.p. 206–208 °C. H NMR (DMSO‑d6, 500 MHz)
Crystal size/mm
Theta range for data collection
Limiting indices
Reflections collected/unique
Completeness to theta=25.00
Max. and min. transmission
Refinement method
0.25×0.22×0.18
2.78 to 25.00°.
–17 ≤h≤17, –9≤k≤9, –20≤l≤22
14569/3705 (Rint = 0.0201)
99.6%
0.9639 and 0.9504
Full‑matrix least‑squares on F 2
3705/0/275
δ 2.43 (m, 1H, 2a‑H), 2.69 (m, 1H, 2b‑H), 2.96 (m, 2H, 4‑H), 3.38 (m,
1H, 3‑H), 5.80 (d, 1H, J=6.0 Hz,11‑H), 6.29 (d, 1H, J=4.0 Hz, 10‑NH),
6.58–7.16 (m, 14H, PhH), 8.84 (s, 1H, 5‑NH). IR (KBr) υ: 3295 m,
1594 m, 1529 s, 1388 m, 754 m, 698 m. Anal. calcd for C25H22N2O: C,
81.94; H, 6.05; N, 7.64; found: C, 81.77; H, 5.83; N, 7.45%. MS (ESI)
m/z: 367.2 (M+1).
Data/restraints/parameters
Goodness‑of‑fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
This work was supported by the National Natural Science
Foundation of China for Young Scholars (Grant No. 21201087),
the Natural Science Foundation of Jiangsu Province (No.
BK20131244) and a start‑up grant from Jiangsu University of
Science and Technology, P.R. of China.
1.015
R1 =0.0507, wR2 = 0.1357
R1 =0.0614, wR2 = 0.1472
0.548 and –0.511
Largest diff. peak and hole/e Å–3
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