Page 7 of 13
RSC Advances
DOI: 10.1039/C5RA06395G
2H), 7.72 –7.68 (m, 1H), 7.53ꢀ7.49 (m, 1H), 6.91 (d, J = 8.4 Hz,
MHz, CDCl3): δ 9.18 (s, 1H), 8.11 (d, J = 8.4 Hz, 1H), 7.89 (s,
1H), 6.73 (d, J = 8.4 Hz, 1H), 4.09 (s, 3H), 3.96 (s, 3H), 3.41ꢀ 60 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.77 (d, J = 6.8 Hz, 1H), 7.72ꢀ7.65
3.37 (m, 2H), 3.31 (dd, J = 5.7, 8.1 Hz, 2H); 13C NMR (100 MHz,
CDCl3); δ 159.8, 151.4, 149.7, 148.7, 148.2, 140.2, 133.8, 130.3,
130.1, 129.6, 129.1, 128.6, 128.5, 128.2, 126.3, 121.6, 107.0,
104.0, 56.5, 56.0, 32.4, 28.3; MS m/z (relative intensity): 343
(m, 2H), 7.48 (t, J = 7.4 Hz, 1H), 7.38 (t, J = 7.6 Hz, 1H), 3.45
(dd, J = 6.0, 8.0 Hz, 2H), 3.24 (t, J = 6.8 Hz, 2H); 13C NMR (100
MHz, CDCl3); δ 160.8, 151.5, 147.8, 144.3, 134.4, 133.6, 132.8,
130.3, 130.2, 129.5, 129.4, 129.3, 128.3, 128.0, 127.2, 126.8,
5
(100); HRMS (ESI+) calcd for C22H19N2O2 ([M+ H]+): 343.1447, 65 126.1, 32.5, 28.0; MS m/z (relative intensity): 317 (100); HRMS
found 343.1451.
(ESI+) calcd for C20H14N235Cl ([M+ H]+): 317.0846, found
317.0843.
4-bromo-6,7-dihydrodibenzo[b,j][1,7]phenanthroline (4p)
Yellow solid; Yield: 90%. m.p. 225ꢀ227 oC, IR [KBr, cmꢀ1] 1652,
2-fluoro-6,7-dihydrodibenzo[b,j][1,7]phenanthroline (4k)
10 Brown solid; Yield: 82%. m.p. 180ꢀ182 oC, IR [KBr, cmꢀ1] 1597,
1566, 1498, 1367, 1215, 990, 825, 755; 1H NMR (400 MHz,
CDCl3): δ 9.23 (s, 1H), 8.16 (d, J = 8.4 Hz, 1H), 8.07ꢀ8.02 (m, 70 1644, 1536, 1134, 998, 929, 785, 743; 1H NMR (400 MHz,
2H), 7.79 (d, J = 8.0 Hz, 1H), 7.73ꢀ7.68 (m, 1H), 7.59 (dd, J = 2.8,
8.8 Hz, 1H), 7.55ꢀ7.46 (m, 2H), 3.41ꢀ3.37 (m, 2H), 3.31 (dd, J =
15 5.8, 7.8 Hz, 2H); 13C NMR (100 MHz, CDCl3); δ 161.7, 159.2,
159.1 (d, J = 2.0 Hz), 151.8, 147.9, 145.4, 134.5, 132.8 (d, J =
CDCl3): δ 9.25 (s, 1H), 8.15 (d, J = 8.4 Hz, 1H), 8.03 (dd, J = 1.2,
7.2 Hz, 1H), 8.00 (s, 1H), 7.95 (dd, J = 1.0, 8.0 Hz, 1H), 7.78 (d,
J = 8.0 Hz, 1H), 7.72ꢀ7.68 (m, 1H), 7.54ꢀ7.50 (m, 1H), 7.37 (t, J
= 7.8 Hz, 1H), 3.49 (dd, J = 5.8, 8.2 Hz, 2H), 3.31 (t, J = 7.0 Hz,
5.0 Hz), 131.1 (d, J = 9.0 Hz), 130.4, 129.6, 129.3 (d, J = 16.0 75 2H); 13C NMR (100 MHz, CDCl3); δ 161.1, 151.7, 147.9, 145.2,
Hz), 128.8 (d, J = 10.0 Hz), 128.4, 127.3, 126.9, 120.4 (d, J =
26.0 Hz), 111.9 (d, J = 21.0 Hz), 32.3, 28.2; MS m/z (relative
20 intensity): 301 (100); HRMS (ESI+) calcd for C20H14N2F ([M+
H]+): 301.1141, found 301.1133.
134.5, 133.9, 133.8, 130.5, 129.6, 129.5, 129.4, 128.9, 128.4,
127.3, 127.0, 126.8, 124.2, 32.6, 28.2; MS m/z (relative
intensity): 361 (100); HRMS (ESI+) calcd for C20H14N279Br ([M+
H]+): 361.0340, found 361.0341.
2-chloro-6,7-dihydrodibenzo[b,j][1,7]phenanthroline (4l)
80 4-methyl-6,7-dihydrodibenzo[b,j][1,7]phenanthroline (4q)
o
o
White solid; Yield: 81%. m.p. 195ꢀ197 C, IR [KBr, cmꢀ1] 2962,
White solid; Yield: 87%. m.p. 164ꢀ166 C, IR [KBr, cmꢀ1]1639,
2848, 1594, 1491, 1244, 1071, 995, 917, 824; 1H NMR (400
25 MHz, CDCl3): δ 9.12 (s, 1H), 8.13 (d, J = 8.4 Hz, 1H), 7.94 (t, J
= 6.8 Hz, 2H), 7.90 (d, J = 2.0 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H),
1597, 1497, 1432, 1262, 1153, 906, 789, 754; 1H NMR (400
MHz, CDCl3): δ 9.23 (s, 1H), 8.17 (d, J = 8.4 Hz, 1H), 7.97 (s,
1H), 7.83 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.71ꢀ7.67
7.70ꢀ7.66 (m, 1H), 7.61 (dd, J = 2.2, 9.0 Hz, 1H), 7.52ꢀ7.48 (m, 85 (m, 1H), 7.56 (d, J = 6.9 Hz, 1H), 7.52ꢀ7.48 (m, 1H), 7.41 (t, J =
1H), 3.37 – 3.33(m, 2H), 3.26 (dd, J = 4.2, 11.0 Hz, 2H); 13C
NMR (100 MHz, CDCl3); δ 160.1, 151.6, 147.9, 146.6, 134.4,
30 132.4, 132.0, 131.1, 130.3, 130.2, 129.5, 129.4, 129.3, 128.7,
128.3, 127.4, 127.3, 126.9, 32.3, 28.1; MS m/z (relative
7.6 Hz, 1H), 3.41 (dd, J = 5.4, 8.4 Hz, 2H), 3.29 (t, J = 6.9 Hz,
2H), 2.85 (s, 3H); 13C NMR (100 MHz, CDCl3); δ 158.7, 152.5,
147.9, 147.4, 136.6, 134.3, 133.6, 130.6, 130.5, 129.5, 129.2,
128.2, 128.1, 127.2, 127.0, 126.6, 126.0, 32.6, 28.5, 18.1; MS
intensity): 317 (100); HRMS (ESI+) calcd for C20H14N2 35Cl ([M+ 90 m/z (relative intensity): 297 (100); HRMS (ESI+) calcd for
H]+): 317.0846, found 317.0843.
C21H17N2 ([M+ H]+): 297.1392, found 297.1387.
2-bromo-6,7-dihydrodibenzo[b,j][1,7]phenanthroline (4m)
2,3-dimethoxy-6,7-dihydrodibenzo[b,j][1,7]phenanthroline
o
35 White solid; Yield: 87%. m.p. 210ꢀ212 C, IR [KBr, cmꢀ1] 1592,
(4r)
1493, 1397, 1259, 1059, 992, 910, 824; 1H NMR (400 MHz,
CDCl3): δ 9.16 (s, 1H), 8.15 (d, J = 8.5 Hz, 1H), 8.11 (d, J = 2.2 95 2835, 1624, 1594, 1504, 1428, 1260, 1016, 748; H NMR (400
Yellow solid; Yield: 74%. m.p. 201ꢀ203 oC, IR [KBr, cmꢀ1] 2932,
1
Hz, 1H), 7.97 (s, 1H), 7.90 (d, J = 8.9 Hz, 1H), 7.78ꢀ7.74 (m, 2H),
7.72ꢀ7.68 (m, 1H), 7.54ꢀ7.50 (m, 1H), 3.38ꢀ3.35 (m, 2H), 3.28 (t,
40 J = 6.9 Hz, 2H); 13C NMR (100 MHz, CDCl3); δ 160.3, 151.6,
147.9, 146.8, 134.5, 133.7, 132.3, 130.8, 130.4, 130.3, 129.6,
MHz, CDCl3): δ 9.15 (s, 1H), 8.13 (d, J = 8.4 Hz, 1H), 7.95 (s,
1H), 7.75 (d, J = 8.0 Hz, 1H), 7.70ꢀ7.65 (m, 1H), 7.52ꢀ7.47 (m,
2H), 7.21 (s, 1H), 4.05 (s, 3H), 4.03 (s, 3H), 3.37ꢀ3.33 (m, 2H),
3.26 (t, J = 7.2 Hz, 2H); 13C NMR (100 MHz, CDCl3); δ 157.5,
129.5, 129.4, 129.3, 128.3, 127.3, 127.0, 120.1, 32.4, 28.1; MS 100 153.4, 152.6, 149.7, 147.8, 145.5, 134.1, 131.7, 130.2, 129.3,
m/z (relative intensity): 361 (100); HRMS (ESI+) calcd for
C20H14N2 79Br ([M+ H]+): 361.0340, found 361.0334.
129.1, 128.0, 127.2, 126.8, 126.4, 123.5, 107.4, 106.2, 56.3, 56.1,
32.0, 28.4; MS m/z (relative intensity): 343 (100); HRMS (ESI+)
calcd for C22H19N2O2 ([M+ H]+): 343.1447, found 343.1447.
6,7-dihydro-[1,3]dioxolo[4',5':4,5]benzo[1,2-j]benzo[b][1,7]
45 2-methyl-6,7-dihydrodibenzo[b,j][1,7]phenanthroline (4n)
White solid; Yield: 78%. m.p. 115 ꢀ 117oC, IR [KBr, cmꢀ1] 1641,
1597, 1496, 1247, 1135, 995, 827, 758; 1H NMR (400 MHz, 105 phenanthroline (4s)
o
CDCl3): δ 9.21 (s, 1H), 8.16 (d, J = 8.5 Hz, 1H), 8.00 (s, 1H),
7.95 (d, J = 8.6 Hz, 1H), 7.77 (t, J = 8.5 Hz, 2H), 7.71 – 7.61 (m,
50 1H), 7.57 – 7.49 (m, 2H), 3.40 – 3.37 (m, 2H), 3.30 (t, J = 6.7 Hz,
2H), 2.55 (s, 3H); 13C NMR (100 MHz, CDCl3); δ 158.9, 152.4,
White solid; Yield: 80%. m.p. 198ꢀ200 C, IR [KBr, cmꢀ1] 1592,
1498, 1466, 1240, 1205, 1038, 943, 844 759; 1H NMR (400 MHz,
CDCl3): δ 9.09 (s, 1H), 8.14 (d, J = 8.4 Hz, 1H), 7.98 (s, 1H),
7.77 (d, J = 7.6 Hz, 1H), 7.70ꢀ7.66 (m, 1H), 7.52ꢀ7.48 (m, 1H),
148.0, 146.9, 136.2, 134.4, 133.0, 132.8, 130.4, 129.5, 129.2, 110 7.35 (s, 1H), 7.22 (s, 1H), 6.12 (s, 2H), 3.34ꢀ3.31 (m, 2H), 3.29ꢀ
128.5, 128.3, 128.2, 127.8, 127.3, 126.7, 32.4, 28.4, 21.7; MS
m/z (relative intensity): 297 (100); HRMS (ESI+) calcd for
55 C21H17N2 ([M+ H]+): 297.1392 found 297.1387.
3.25 (m, 2H); 13C NMR (100 MHz, CDCl3); δ 157.7, 152.5, 151.7,
147.9, 147.8, 146.9, 134.3, 132.4, 130.3, 129.4, 129.2, 128.2,
127.3, 126.9, 126.6, 125.0, 105.4, 103.9, 101.9, 32.0, 28.5; MS
m/z (relative intensity): 327 (100); HRMS (ESI+) calcd for
4-chloro-6,7-dihydrodibenzo[b,j][1,7]phenanthroline (4o)
o
White solid; Yield: 91%. m.p. 226ꢀ228 C, IR [KBr, cmꢀ1] 1648, 115 C21H15N2O2 ([M+ H]+): 327.1134, found 327.1136.
1633, 1496, 1428, 1321, 1006, 928, 789, 747; 1H NMR (400
2,10-difluoro-6,7-dihydrodibenzo[b,j][1,7]phenanthroline (4t)
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