(10 mL) was stirred at reflux for 1 d. The reaction was cooled to
the room temperature, the yellow precipitate was filtered, stirred
for 1.5 h in CH2Cl2 to dissolve the rest of the starting materials,
filtered off, and dried in vacuo, yielding (0,17 g 50%) of a yellow
solid. mp 356 ◦C; IR (KBr): 3056m, 3010m, 2229w, 1924w, 1862w,
1590s, 1527w, 1479s, 1457w, 1435w, 1419s, 1396s, 1378s, 1353m,
1334s, 1297m, 1233m, 1178w, 1117m, 1103m, 1086s, 1071s, 1009s,
985m, 948m, 835s, 812m, 784s, 746m, 728s, 674m, 651m, 631w,
590w, 568w, 527s, 514m, 503w, 461m, 451m, 415w; 1H-NMR
798m, 788s, 773m, 743m, 693w, 655w, 615w, 606w, 540w, 506w,
1
3
438w; H-NMR (400 MHz, CD2Cl2), 8.0 (d, 1H, J = 8.4 Hz),
7.5 (d, 1H, 3J = 8.4 Hz), 6.2 (s, 1H, pyrazol), 6.2 (s, 1H, pyrazol),
2.5 (s, 1H, CH3), 2.3 (s, 1H, CH3), 2.1 (s, 1H, CH3); 13C-NMR
◦
(500 MHz, nitrobenzene-d5, 140 C), 150.9, 150.3, 142,9, 141.6,
135.1, 133.9, 131.9, 130.7, 128.0, 126.8, 107.7, 19,4, 12.7, 11.0;
(600 MHz, CD2Cl2), 150.6, 150.6, 142.8, 141.7, 135.3, 133.2, 132.2,
131.2, 127.7, 126.7, 107.8, 19.7, 13.4, 11.7; MS (EI) m/z (%): 420
(M+, 11), 405 (100), 195 (7%).
3
(400 MHz, CDCl3) d 8.1 (d, 1H, J = 8.0 Hz), 7.87–7.89 (m,
3H), 7.79–7.81 (m, 2H), 7.6 (dd, 1H, 3J = 8.4, 8.4 Hz); 13C-NMR
(600 MHz, CDCl3), 155,5, 136.4, 134.1, 132.5, 132.3, 132.0, 131.2,
131.0, 130,2, 128.5, 126.8, 124.4; MS (EI) m/z (%): 514 (M+, 100),
486 (18), 405 (18), 326 (73), 243 (M2+,13), 163, (41), 149, (10%).
7,10-Di(thiophen-2-yl)-8,9-diazafluoranthene (8a). A mixture
of 3,6-di(thiophen-2-yl)-1,2,4,5-tetrazine (0.32 g, 1.32 mmol) and
acenaphthylene (0.10 g, 0.66 mmol) in 1,2-dichloroethane (10 mL)
was stirred at reflux for 4 d. The yellow precipitate was filtered,
washed thoroughly with methanol and dried in vacuo, yielding
(0.095 g, 39%). mp 220 ◦C (dec); IR (KBr): 3102s (br.), 3058s,
2582m (br.), 1811w, 1695w, 1630m, 1607m, 1579m, 1554m, 1506w,
1485m, 1458m, 1418s, 1379s, 1333s, 1311s, 1221m, 1187m, 1111s,
990w, 928w, 852s, 826s, 785m, 775s, 741m, 698s, 669w, 618s, 518w,
501w; 1H-NMR (300 MHz, CDCl3) d 8.3 (d, 1H, 3J = 7.2 Hz), 8.1
(d, 1H, 3J = 8.1 Hz), 7.9 (d, 1H, 3J = 3.0 Hz), 7.66–7.71 (m, 2H),
7,10-Bis(4-bromophenyl)-1,6-dimethyl-8,9-diazafluoranthene
(6b).
A mixture of 2,7-dimethylacenaphthylene (0.050 g,
0.28 mmol) and 3,6-bis(4-bromophenyl)-1,2,4,5-tetrazine (0.22 g,
0.56 mmol) in p-xylene (5 mL) was stirred in an autoclave (600
Psi) at 180 ◦C for 2 d. The solvent was evaporated, the residue was
washed thoroughly with acetone and dried in vacuo to yield a light
yellow solid (0.05 g, 33%). mp 310 ◦C (dec); IR (KBr): 3055w,
2995w, 2956w, 2916w, 2236w, 1970w, 1899w, 1638m, 1608m,
1595s, 1563m, 1503 1479s, 1446s, 1412s, 1391s, 1374s, 1347m,
1331s, 1318m, 1293w, 1206m, 1183m, 1154s, 1108s, 1066s, 1030m,
1007s, 854s, 834s, 811m, 795m, 740m, 726m, 678m, 626m, 546m,
3
7.3 (dd, 1H, J = 4.8, 4.8 Hz); 13C-NMR (400 MHz, CDCl3) d
150.9, 139.8, 134.1, 132.7, 132.1, 131.4, 130.5, 129.5, 129.3, 128.8,
127.9, 127,1; MS (EI) m/z (%): 368 (M+, 100), 340 (62), 295 (24),
248 (14), 170 (11%).
1
3
534m, 445m; H-NMR (300 MHz, CDCl3) d 7.9 (d, 1H, J =
8.1 Hz), 7.68 (s, 4H, 4-bromophenyl), 7.4 (d, 1H, 3J = 8.1 Hz), 2.0
(s, 3H, CH3); 13C-NMR (400 MHz, CDCl3) d 154.8, 139.7, 139.2,
135.8, 133.5, 132.5, 132.4, 131.8, 130.5, 130.3, 127.1, 124.1, 23.63;
MS (EI) m/z (%): 542 (M+, 100), 514 (42), 420 (46), 353 (26), 276
(22), 169 (M 2+ (43%)).
7,10-Di(thiophen-2-yl)-1,6-dimethyl-8,9-diazafluoranthene (8b).
A mixture of 2,7-dimethylacenaphthylene (0.05 g, 0.28 mmol)
and 3,6-di(thiophen-2-yl)-1,2,4,5-tetrazine (0.14 g, 0.56 mmol) in
p-xylene (5 mL) was stirred at 180 ◦C in an autoclave (600 Psi)
for 3 d. The solvent was evaporated, the residue was purified
by column chromatography (silica gel, hexane/ethyl acetate 5:1,
hexane/acetone 5:1) to yield a yellow solid (0.065 g, 59%). mp
260 ◦C (dec); IR (KBr): 3107w, 3022w, 3004w, 2913w, 2250w,
1788w, 1612m, 1573w, 1550w, 1498m, 1443m, 1404s, 1375s, 1332s,
1315m, 1220w, 1202m, 1174w, 1155w, 1094m, 1055m, 1039m,
987w, 974w, 900w, 853s, 832m, 798w, 769m, 693s, 637w, 606w,
541w; 1H-NMR (400 MHz, CDCl3) d 7.9 (d, 1H, 3J = 8.4 Hz), 7.5
(dd, 1H, 4J = 1.2, 3J = 5.2 Hz), 7.4 (d, 1H, 3J = 8.4 Hz), 7.3 (dd,
1H, 4J = 0.8, 3J = 3.2 Hz), 7.2 (dd, 1H, 3J = 3.6, 5.2 Hz), 2.2 (s, 3H,
CH3); 13C-NMR (400 MHz, CDCl3) d 149.9, 141.8, 139.6, 136.2,
132.4, 130.4, 130.3, 129.8, 128.7, 127.7, 127.0, 23.3; MS (EI) m/z
(%): 396 (M+, 100), 368 (41), 353 (40), 319 (18%).
7,10-Bis(3,5-dimethyl-1H-pyrazol-1-yl)-8,9-diazafluoranthene
(7a).
A
mixture of 3,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-
1,2,4,5-tetrazine (0.18 g, 0.66 mmol) and acenaphthylene (0.050
g, 0.33 mmol) in dichloromethane (10 mL) was stirred at reflux for
3 d. The solvent was evaporated, the residue was purified by
column chromatography (silica gel, hexane/ethyl acetate, 5:1)
to yield a light yellow solid (0.1 g, 78%). mp 203 ◦C (dec);
IR (KBr): 3055w, 2978w, 2921m, 2856w, 1560s, 1537m, 1488w,
1466m, 1439m, 1419s, 1284w, 1264w, 1231w, 1184w, 1146w,
1091m, 1043m, 1022m, 988w, 968m, 823m, 770s, 760s, 746m, 698w,
1
676w, 632w, 571w, 502w; H-NMR (500 MHz, CDCl3) d 8.1 (d,
1H, 3J = 8.0 Hz), 8.0 (d, 1H, 3J = 7.0 Hz), 7.7 (dd, 1H, 3J = 7.7,
7,7 Hz), 6.2 (s, 1H, pyrazol), 2.5 (s, 1H, CH3), 2.4 (s, 1H, CH3);
13C-NMR (75 MHz, CDCl3) d 150.8, 150.6, 142.1, 134.3, 131.9,
131.2, 130.5, 129.5, 129.1, 128.5, 108,0, 13.6, 12.1; MS (EI) m/z
(%): 392 (M+, 74), 391 (M+ - 1, 100), 393 (M+ + 1, 19%).
7,10-Di(furan-2-yl)-8,9-diazafluoranthene (9a). A mixture of
acenaphthylene (0.05 g, 0.33 mmol) and 3,6-di(furan-2-yl)-1,2,4,5-
tetrazine (0.14 g, 0.66 mmol) in chlorobenzene (10 mL) was stirred
at reflux for 2 d. The solvent was evaporated, the residue was
purified by column chromatography (aluminium oxide, hexane).
Note: evaporation of solvent should be carried out below 30 ◦C
(decomposition of product). Yield (0.08 g, 73%) of a yellow solid.
mp 150 ◦C; IR (KBr): 3138w, 3059w, 2924m, 2853w, 1599m,
1529w, 1490m, 1476s, 1421s, 1398s, 1323s, 1217m, 1181w, 1161m,
1129s, 1104w, 1071w, 1055m, 1012s, 888s, 827s, 810s, 773s, 728s,
7,10-Bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,6-dimethyl-8,9-diaza-
fluoranthene (7b).
A
mixture of 3,6-bis(3,5-dimethyl-1H-
pyrazol-1-yl)-1,2,4,5-tetrazine (0.15 g, 0.56 mmol) and 2,7-
dimethylacenaphthylene (0.050 g, 0.28 mmol) in mesitylene (8 mL)
was stirred at reflux for 1 d. The mixture was cooled to the room
temperature, the precipitate was filtered, washed thoroughly with
acetone and dried in vacuo to yield a yellow solid (0.1 g 85%). mp
350 ◦C; IR (KBr): 3014w, 2961w, 2925m, 2860w, 1614w, 1554s,
1505s, 1462s, 1414s, 1398s, 1375s, 1348m, 1274w, 1202m, 1195m,
1157w, 1139w, 1102s, 1071m, 1034m, 1023m, 977w, 859s, 811w,
1
3
628w, 592m; H-NMR (400 MHz, CDCl3) d 8.8 (d, 1H, J =
7.2 Hz), 8.3 (d, 1H, 3J = 8.4 Hz), 8.1 (dd, 1H, 4J = 0.6, 3J = 1.6 Hz,
furyl), 7.9 (dd, 1H, 3J = 7.8, 7.8. Hz), 7.5 (dd, 1H, 4J = 1.2, 3J =
3
3.6 Hz, furyl), 6.9 (dd, 1H, J = 1.6, 3.2 Hz, furyl); 13C-NMR
(400 MHz, acetone-d6) d 152.0, 145.9, 144,4, 132, 131.82, 131.8,
Org. Biomol. Chem., 2009, 7, 2082–2092 | 2087
This journal is
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