Table 5 Synthesis of oxa-aza-phenanthrene and anthracene derivatives
(Scheme 3)
(11-C), 128.9 (arom-C), 129.1 (arom-C), 129.5 (arom-C), 129.9
(arom-C), 133.8 (7a-C), 134.2 (11a-C), 136.1 (6-C), 139.6
(arom-C), 167.1 (arom-C), 183.7(CO). EIMS (m/z): 397(M)+.
Anal. Calc. for C26H23NO3; C, 78.57; H, 5.83; N, 3.52. Found:
C, 78.60; H, 5.82; N, 3.49.
Time
Epoxide (min)
Yield
%
Entry Isoquinoline R1
Product
1
2
3
4
5
6
7
8
1
1
1
1
1
1
1
1
H
NO2
OCH3 3a
Cl
H
NO2
OCH3 3b
Cl
3a
3a
20
15
25
18
45
30
50
40
4a
4b
4c
4d
4e
4f
95
98
91
96
93
96
90
95
(4-Chloro-phenyl)-(3-phenyl-2,3-dihydro-1H,4aH-4-oxa-10a-aza-
phenanthren-1-yl)-methanone (4d)
3a
3b
3b
IR (KBr) (νmax/cm−1) 3100, 1605, 1580, 1525, 1470, 1035, 670.
1H NMR (400 MHz, CDCl3) δH (ppm) 3.43 (s, 1H, 11b-H),
4g
4h
3b
3.65 (m, 2H, 3-Ha & 3-Hb), 3.95 (dd, 1H, J3Ha,
= 7.5,
2H
J3Hb, 2H = 2.3Hz, CH), 4.13 (dd, 1H, J3Ha, 4H = 7.7, J3Hb, 4H
=
2.4 Hz, CH), 5.17 (d, 1H, J7H,4H = 6.6, 7-H), 6.95–7.42
(m, 10H, 8-H, 6-H, Ar–H), 7.96–8.01 (m, 2H, Ar–H), 7.42–7.45
(m, 2H, Ar–H). 13C NMR (100 MHz, CDCl3) δc (ppm) 38.3
(3-C), 63.5 (4-C), 72.5 (2-C), 84.8 (11b-C), 102.1 (7-C), 125.1
(arom-C), 126.6 (8-C), 127.1 (11-C), 127.5 (10-C), 127.9 (9-C),
128.2 (arom-C), 128.9 (arom-C), 129.6 (arom-C), 130.1
(arom-C), 132.6(6-C), 133.9 (arom-C), 134.1 (11a-C), 135.4
(7a-C), 137.9 (arom-C), 138.9 (arom-C), 184.3 (CO). EIMS
(m/z): 401(M)+, 403 (M + 2)+. Anal. Calc. for C25H20ClNO2;
C, 74.71; H, 5.02; N, 3.49. Found: C, 74.76; H, 4.96; N, 3.56.
Scheme 3
(arom-C), 128.9 (arom-C), 129.4 (arom-C), 132.4 (arom-C),
134.3 (7a-C), 134.8 (11a-C), 135.2 (arom-C), 137.8 (6-C), 139.2
(arom-C), 183.2 (CO). EIMS (m/z): 367(M)+. Anal. Calc for
C25H21NO2; C, 81.72; H, 5.76; N, 3.81. Found: C, 81.68; H,
6.79; N, 3.83.
(7a,8,9,10,11,11a-Hexahydro-7H,12aH-12-oxa-6a-aza-benzo[a]
anthracen-7-yl)-phenyl-methanone (4e)
IR (KBr) (νmax/cm−1) 3032, 2937, 2862, 1630, 1580, 1430,
1030. 1H NMR (400 MHz, CDCl3) δH (ppm) 1.40–1.47 (m, 4H,
2′-H & 3′-H), 1.56–1.88 (m, 4H, 1′-H & 4′-H), 3.06 (ddd, 1H,
JH1′a = 11.4, JH3 = 11.1, JH1′b = 3.5 Hz, 2-H), 3.52 (s, 1H, 11b-
H), 3.80 (d, 1H, JH3 = 2.9 Hz, 4-H), 4.18–4.23 (m, 1H, 3-H),
5.13 (d, 1H, JH6 = 6.8 Hz, 7-H), 6.90–7.20 (m, 8H, Ar–H), 8.03
(d, 2H, J = 6.2 Hz, Ar–H). 13C NMR (100 MHz, CDCl3) δc
(ppm) 19.2 (4′-C), 20.4 (2′-C), 23.5 (3′-C), 29.8 (1′-C), 33.6 (3-
C), 65.3 (4-C), 69.4 (2-C), 84.1 (11b-C), 102.2 (7-C), 126.1 (8-
C), 126.6 (9-C), 127.3 (10-C), 127.9 (arom-C), 128.1 (11-C),
128.5 (arom-C), 132.6 (7a-C), 133.9 (arom-C), 134.3 (11a-C),
135.4 (6-C), 137.1 (arom-C), 183.6 (CO). EIMS (m/z): 345(M)+.
Anal. Calc. for C23H23NO2; C, 79.97; H, 6.71; N, 4.05. Found:
C, 79.94; H, 6.69; N, 4.07.
(4-Nitro-phenyl)-(3-phenyl-2,3-dihydro-1H,4aH-4-oxa-10a-aza-
phenanthren-1-yl)-methanone (4b)
IR (KBr) (νmax/cm−1) 3100, 1605, 1580, 1525, 1520, 1470,
1340, 1035. 1H NMR (400 MHz, CDCl3) δH (ppm) 3.45, (s, 1H,
11b-H,), 3.67 (m, 2H, 3-Ha & 3-Hb), 3.96 (dd 1H, J3Ha, 2H = 7.4
Hz, J3Hb, 2H = 2.8 Hz, CH), 4.16 (dd, 1H, J3Ha, 4H = 7.6 Hz,
J3Hb,
= 2.5 Hz, CH), 5.19 (d, 1H, J7H,4H = 6.7, 7-H),
4H
6.92–7.30 (m, 10H, 8-H, 6-H, Ar–H), 8.12–8.33 (m, 4H, Ar–H).
13C NMR (100 MHz, CDCl3) δc (ppm) 38.4 (3-C), 63.9 (4-C),
72.2 (2-C), 84.9 (11b-C), 104.6 (7-C), 123.9 (9-C), 126.8 (8-C),
127.3 (10-C), 128.4 (11-C), 128.9 (arom-C), 129.4 (arom-C),
129.9 (arom-C), 130.1 (arom-C), 130.5 (arom-C), 134.8 (11a-C),
135.2 (7a-C), 137.8 (6-C), 139.2 (arom-C), 143.9 (arom-C),
153.1 (arom-C), 183.4 (CO). EIMS (m/z): 412(M)+. Anal. Calc.
for C25H20N2O4; C, 72.80; H, 4.89; N, 6.79. Found: C, 72.76;
H, 4.92; N, 6.77.
(7a,8,9,10,11,11a-Hexahydro-7H,12aH-12-oxa-6a-aza-benzo[a]
anthracen-7-yl)-(4-nitro-phenyl)-methanone (4f)
IR (KBr) (νmax/cm−1) 3035, 2940, 2862, 1638, 1580, 1530,
1445, 1345, 1045. 1H NMR (400 MHz, CDCl3) δH (ppm)
1.42–1.50 (m, 4H, 2′-H & 3′-H), 1.59–1.90 (m, 4H, 1′-H & 4′-
H), 3.16 (ddd, 1H, JH1′a = 11.6, JH3 = 11.3, JH1′b = 3.6 Hz, 2-H),
3.58 (s, 1H,11b-H), 3.88 (d, 1H, J = 2.8 Hz, 4-H), 4.20–4.27 (m,
1H, 3-H), 5.16 (d, 1H, J = 6.8 Hz), 6.93–7.15 (m, 5H, Ar–H),
8.14–8.35 (m, 4H, Ar–H). 13C NMR (100 MHz, CDCl3) δc
(ppm) 18.6 (4′-C), 20.6(2′-C), 23.7 (3′-C), 29.7(1′-C), 33.8 (3-
C), 65.6 (4-C), 69.1 (2-C), 84.2(11b-C), 102.8 (7-C), 122.8
(arom-C), 126.3 (8-C), 126.9 (9-C), 127.7 (10-C), 128.1 (11-C),
128.8 (arom-C), 132.6 (7a-C), 134.6 (11a-C), 135.7 (6-C), 144.1
(arom-C), 153.1 (arom-C), 184.4 (CO). EIMS (m/z): 390 (M)+.
Anal. Calc. for C23H22N2O4; C, 79.97; H, 6.71; N, 4.05. Found:
C, 79.94; H, 6.69; N, 4.07.
(4-Methoxy-phenyl)-(3-phenyl-2,3-dihydro-1H,4aH-4-oxa-10a-
aza-phenanthren-1-yl)-methanone (4c)
IR (KBr) (νmax/cm−1) 3050, 2830, 1605, 1580, 1510, 1450,
1
1045. H NMR (400 MHz, CDCl3) δH (ppm) 3.39 (s, 1H, 11b-
H), 3.60 (m, 2H, 3-Ha & 3-Hb), 3.84 (s, 3H, OCH3), 3.87 (dd,
1H, J3Ha,
= 7.4, J3Hb,
= 2.5 Hz, CH), 4.09 (dd, 1H,
2H
2H
J3Ha, 4H = 7.6, J3Hb, 4H = 2.2 Hz, CH), 5.13 (d, 1H, J7H,4H
=
6.9 HZ, 7-H), 6.94–6.97 (m, 2H, Ar–H), 7.01–7.39 (m, 10H,
8-H, 6-H, Ar–H), 8.01–8.05 (m, 2H, Ar–H). 13C NMR
(100 MHz CDCl3) δc (ppm) 38.2 (3-C), 56.4 (OCH3), 63.1
(4-C), 71.7 (2-C), 83.9 (11b-C), 102.8 (7-C), 113.9 (arom-C),
125.7 (arom-C), 126.3 (8-C), 126.8 (9-C), 127.6 (10-C), 128.4
904 | Green Chem., 2012, 14, 901–905
This journal is © The Royal Society of Chemistry 2012