1692
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 9, September, 2018
Shevchenko et al.
6-Fluoro-11,13-dimethylpyrimido[5´,4´:3,4]pyrrolo[1,2-f]-
phenanthridine-12,14(11H,13H)-dione (3e). The yield was 60 mg
(86%), colorless needles, m.p. >330 °C (DMF). HRMS, found:
m/z 348.1143 [M + H]+. C20H15N3O2F+. Calculated: 348.1143.
1H NMR (500 MHz, CDCl3), δ: 3.55 (s, 3 H, Me); 3.57 (s, 3 H,
6,8,11,13-Tetramethylpyrimido[5´,4´:3,4]pyrrolo[1,2-f]phen-
anthridine-12,14(11H,13H)-dione (3i). The yield was 59 mg
(83%), colorless needles, m.p. 287—289 °C (dec., DMSO).
HRMS, found: m/z 358.1548 [M + H]+. C22H20N3O2+. Cal-
culated: 358.1550. 1H NMR (500 MHz, CDCl3), δ: 2.51 (s, 3 H,
Me); 2.86 (s, 3 H, Me); 3.43 (s, 3 H, NMe); 3.49 (s, 3 H, NMe);
Me); 7.38 (s, 1 H, H(10)); 7.39 (m, 1 H, HAr); 7.67 (t, 1 H, HAr
,
J = 7.0 Hz); 7.75 (t, 1 H, HAr, J = 7.3 Hz); 7.95 (m, 1 H, HAr);
8.15 (m, 1 H, HAr); 8.31 (d, 1 H, HAr, J = 8.2 Hz); 10.37 (d, 1 H,
HAr, J = 8.2 Hz). 1H NMR (400 MHz, CDCl3 + CF3COOH
(3 : 1)), δ: 3.64 (s, 3 H, Me); 3.82 (s, 3 H, Me); 6.33 (br.s, 2 H,
C(10)H2); 7.33 (m, 1 H, HAr); 8.12 (t, 1 H, HAr, J = 7.7 Hz);
8.19 (m, 1 H, HAr); 8.34 (t, 1 H, HAr, J = 7.7 Hz); 8.42 (m, 1 H,
HAr); 8.75 (d, 1 H, HAr, J = 8.3 Hz); 10.32 (d, 1 H, HAr, J = 8.3 Hz).
13C{1H} NMR (100 MHz, CDCl3 + CF3COOH (3 : 1)), δ: 30.2,
7.23 (s, 1 H, HAr); 7.50 (s, 1 H, H(10)); 7.57 (t, 1 H, HAr,
J = 8.1 Hz); 7.62 (t, 1 H, HAr, J = 8.1 Hz); 8.11 (s, 1 H, HAr);
8.32 (d, 1 H, HAr, J = 8.2 Hz); 10.20 (d, 1 H, HAr, J = 8.2 Hz).
13C{1H} NMR (126 MHz, CDCl3), δ: 21.3, 25.0, 28.8, 31.6, 99.0,
100.6, 122.2, 122.3, 124.2, 124.6, 126.3, 127.0, 128.2, 128.2, 128.4,
130.1, 130.8, 131.6, 134.7, 134.8, 151.6, 160.3.
5,7,11,13-Tetramethylpyrimido[5´,4´:3,4]pyrrolo[1,2-f]phen-
anthridine-12,14(11H,13H)-dione (3j). The yield was 64 mg
(89%), colorless thin needles, m.p. 315—317 °C (dec., DMF).
HRMS, found: m/z 358.1547 [M + H]+. C22H20N3O2+. Cal-
culated: 358.1550. 1H NMR (500 MHz, CDCl3), δ: 2.54 (s, 3 H,
Me); 2.99 (s, 3 H, Me); 3.51 (s, 3 H, NMe); 3.52 (s, 3 H, NMe);
7.26 (s, 1 H, H(10)); 7.21 (s, 1 H, HAr); 7.50—7.70 (m, 3 H, HAr);
8.48 (d, 1 H, HAr, J = 8.2 Hz); 10.29 (d, 1 H, HAr, J = 8.4 Hz).
13C{1H} NMR (100 MHz, CDCl3 + CF3COOH (3 : 1), some
signals were broadened and melted into the background), δ: 21.2,
26.42, 30.3, 34.9, 115.1, 121.4, 121.7, 127.4, 129.1, 133.6, 133.7,
136.2, 136.7, 137.2, 137.5, 138.3, 144.1, 151.2, 157.5.
3
34.8, 110.1, 110.3, 119.9, 121.7, 123.4, 125.7 (d, JC,F = 9 Hz);
128.7, 130.9, 133.7, 137.8, 150.9.
6-Methoxy-11,13-dimethylpyrimido[5´,4´:3,4]pyrrolo[1,2-f]-
phenanthridine-12,14(11H,13H)-dione (3f). The yield was 56 mg
(78%), colorless prisms, m.p. 286—288 °C (dec., DMF). HRMS,
found: m/z 360.1345 [M + H]+.C21H18N3O3+. Calculated:
360.1343. 1H NMR (500 MHz, CDCl3), δ: 3.50 (s, 3 H, NMe);
3.52 (s, 3 H, NMe); 4.01 (s, 3 H, OMe); 7.25 (s, 1 H, H(10));
7.22 (dd, 1 H, HAr, J = 9.2 Hz, J = 2.3 Hz); 7.63 (t, 1 H, HAr
J = 7.4 Hz); 7.69 (t, 1 H, HAr, J = 7.7 Hz); 7.80 (s, 1 H, HAr
J = 9.1 Hz); 7.86 (d, 1 H, HAr, J = 2.5 Hz); 8.32 (d, 1 H, HAr
,
,
,
5,7-Difluoro-11,13-dimethylpyrimido[5´,4´:3,4]pyrrolo[1,2-f]-
phenanthridine-12,14(11H,13H)-dione (3k). The yield was 48 mg
J = 8.0 Hz); 10.30 (d, 1 H, HAr, J = 8.1 Hz). 1H NMR (500 MHz,
CDCl3 + CF3COOH (3 : 1)), δ: 3.61 (s, 3 H, NMe); 3.77 (s, 3 H,
NMe); 4.09 (s, 3 H, OMe); 6.29 (br.s, 2 H, C(10)H2); 7.59 (dd,
1 H, HAr, J = 9.3 Hz, J = 2.4 Hz); 8.00—8.12 (m, 3 H, HAr);
8.27 (t, 1 H, HAr, J = 7.7 Hz); 8.74 (d, 1 H, HAr, J = 8.4 Hz);
10.46 (d, 1 H, HAr, J = 8.4 Hz). 13C{1H} NMR (100 MHz, CDCl3 +
+ CF3COOH (3 : 1), some signals were broadened and melted
into the background), δ: 30.2, 34.8, 56.3, 106.3, 119.0, 121.3,
122.2, 123.3, 125.6, 126.9, 130.5, 133.6, 137.6, 150.9, 157.2, 160.6.
6-Diethylamino-11,13-dimethylpyrimido[5´,4´:3,4]pyrrolo-
[1,2-f]phenanthridine-12,14(11H,13H)-dione (3g). The yield was
64 mg (80%), light-yellow needles, m.p. 229—231 °C (DMF).
HRMS, found: m/z 401.1965 [M + H]+. C25H24N4O2+. Cal-
culated: 401.1972. 1H NMR (500 MHz, CDCl3), δ: 1.10—1.40
(64%), colorless thin needles, m.p. 314—319 °C (dec., DMF).
HRMS, found: m/z 366.1048 [M + H]+. C20H14N3O2F2
.
+
Calculated: 366.1049. 1H NMR (500 MHz, CDCl3), δ: 3.53
(s, 6 H, 2 Me); 7.02—7.12 (m, 1 H, HAr); 7.38—7.44 (m, 1 H,
HAr);7.61—7.76 (m, 3 H, HAr); 8.74—8.79 (m, 1 H, HAr); 10.34
(d, 1 H, HAr, J = 7.8 Hz). 13C NMR spectrum was not recorded
due to the insufficient solubility of compound.
5,7-Dimethoxy-11,13-dimethylpyrimido[5´,4´:3,4]pyrrolo-
[1,2-f]phenanthridine-12,14(11H,13H)-dione (3l). The yield was
62 mg (79%), colorless thin needles, m.p. > 330 °C (dec., DMF).
HRMS, found: m/z 390.1448 [M + H]+. C22H20N3O4+. Cal-
culated: 390.1448. 1H NMR (500 MHz, CDCl3), δ: 3.50 (s, 3 H,
Me); 3.53 (s, 3 H, Me); 4.01 (s, 3 H, OMe); 4.11 (s, 3 H, OMe);
6.67 (s, 1 H, HAr); 6.90 (s, 1 H, HAr); 7.19 (s, 1 H, H(10));
7.55—7.68 (m, 2 H, HAr); 9.31 (d, 1 H, HAr, J = 8.9 Hz); 10.35
(s, 1 H, HAr). 13C{1H} NMR (126 MHz, CDCl3 + CF3COOH
(3 : 1), some signals were broadened and melted into the back-
ground), δ: 29.9, 34.4, 55.9, 56.4, 91.2, 100.8, 107.9, 109.5, 119.6,
127.2, 128.0, 132.5, 134.9, 136.2, 138.0, 150.7, 157.0, 160.8, 163.4.
12,14-Dimethylbenzo[c]pyrimido[5´,4´:3,4]pyrrolo[1,2-f]-
phenanthridine-11,13(12H,14H)-dione (3m). The yield was 30 mg
(40%), light-yellow flaky powder, m.p. 278—282 °C (dichloro-
ethane—DMSO). HRMS, found: m/z 380.1397 [M + H]+.
C24H18N3O2+. Calculated: 380.1394. 1H NMR (400 MHz,
CDCl3), δ: 3.52 (s, 3 H, Me); 3.54 (s, 3 H, Me); 7.60—7.75
(m, 4 H, HAr); 7.90 (d, 1 H, HAr, J = 8.8 Hz); 7.98—8.03 (m, 1 H,
HAr); 8.05 (s, 1 H, H(15)); 8.34—8.44 (m, 2 H, HAr); 8.95—9.03
(m, 1 H, HAr); 10.25 (d, 1 H, HAr, J = 8.1 Hz). 13C{1H} NMR
(126 MHz, CDCl3), δ: 28.8, 31.9, 99.6, 100.6, 120.6, 121.0, 122.4,
122.6, 124.4, 124.6, 126.6, 126.7, 126.9, 127.2, 128.1, 128.3, 128.5,
128.7, 129.1, 131.4, 132.6, 134.2, 151.8, 160.2.
(m, 6 H, 2 NCH2CH3); 3.37—3.60 (m, 10 H, 2 NCH2CH3
+
+ 2 NMe); 7.02 (s, 1 H, HAr); 7.19 (s, 1 H, H(10)); 7.50—7.75
(m, 4 H, HAr); 8.30 (s, 1 H, HAr); 10.25 (d, 1 H, HAr, J = 7.9 Hz).
1H NMR (500 MHz, DMSO-d6), δ: 1.22 (t, 6 H, 2 NCH2CH3,
J = 7.0 Hz); 3.35 (s, 3 H, NMe); 3.47 (s, 3 H, NMe); 3.56 (q, 4 H,
2 NCH2CH3, J = 7.0 Hz); 7.16 (d, 1 H, HAr, J = 9.4 Hz);
7.58—7.71 (m, 3 H, HAr); 8.12 (s, 1 H, HAr); 8.19 (d, 1 H, HAr
,
J = 9.3 Hz); 8.57 (d, 1 H, HAr, J = 8.5 Hz); 10.19 (d, 1 H, HAr
,
J = 8.7 Hz). 13C{1H} NMR (126 MHz, DMSO-d6), δ: 12.4, 28.2,
31.6, 43.8, 97.0, 98.5, 103.4, 115.0, 117.8, 121.9, 122.5, 122.6,
124.1, 126.0, 126.4, 127.4, 127.6, 127.9, 132.2, 145.5, 150.7, 159.4.
5,8,11,13-Tetramethylpyrimido[5´,4´:3,4]pyrrolo[1,2-f]phen-
anthridine-12,14(11H,13H)-dione (3h). The yield was 61 mg
(86%), colorless needles, m.p. 272—274 °C (dec., DMSO).
HRMS, found: m/z 358.1550 [M + H]+. C22H20N3O2+. Cal-
culated: 358.1550. 1H NMR (500 MHz, CDCl3), δ: 2.87 (s, 3 H,
Me); 2.94 (s, 3 H, Me); 3.50 (s, 3 H, NMe); 3.52 (s, 3 H, NMe);
7.20—7.35 (m, 2 H, HAr); 7.45 (s, 1 H, H(10)); 7.53 (t, 1 H, HAr
,
J = 7.4 Hz); 7.63 (t, 1 H, HAr, J = 7.6 Hz); 8.30 (d, 1 H, HAr
,
12,14-Dimethylbenzo[a]pyrimido[5´,4´:3,4]pyrrolo[1,2-f]-
phenanthridine-11,13(12H,14H)-dione (3n). The yield was 54 mg
(71%), colorless thin needles, m.p. 280—282 °C (dec., DMF).
HRMS, found: m/z 380.1393 [M + H]+. C24H18N3O2+. Cal-
culated: 380.1394. 1H NMR (500 MHz, CDCl3), δ: 3.53 (s, 6 H,
J = 8.2 Hz); 10.02 (d, 1 H, HAr, J = 8.2 Hz). 13C{1H} NMR
(126 MHz, CDCl3), δ: 24.1, 25.7, 28.7, 31.7, 99.0, 100.7, 123.3,
125.0, 125.1, 126.9, 127.4, 127.7, 128.1, 128.4, 128.9, 130.9, 131.7,
131.8, 133.4, 133.7, 151.8, 160.4.