The Journal of Organic Chemistry
Page 6 of 9
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836, 795, 765, 747, 699, 671, 629, 578, 557, 543, 513, 483, 468, 437,
C14H679Br81BrCl2 403.8187, found 403.8190; Anal. calcd for
422, 401 cm-1; HRMS (EI) m/z [M]+ calcd for C14H8Cl2I2 499.8087,
C14H679Br81BrCl2: C, 41.53; H, 1.49. Found: C, 41.30; H, 1.63.
found 499.8072.
2,3-Dibromo-6,7-diiodoanthracene (8-Br2-I2).
850 mg
2,3-Dibromoanthracene (8-H2-Br2).
850 mg
(2.51 mmol,
(2.51 mmol, 1.00 eq.) 6-Br2-I2 and 628 mg (2.77 mmol, 1.10 eq.)
DDQ were dissolved in 30 mL of toluene and refluxed for 4 h. The
completion of the reaction was monitored by GCMS. After the
solvent was reduced the remaining solid was washed with
MeOH/EtOH. Crystallization from boiling toluene afforded 679 mg
(2.01 mmol, 80%) of 8-Br2-I2 as a pale yellow solid. Mp dec. >
330 °C; 1H NMR (pyr-d5, 500 MHz, 373 K) δ 8.73 (s, 2 H), 8.41 (s, 2
H), 8.25 (s, 2 H); 13C{1H} NMR (pyr-d5, 126 MHz, 373 K) δ 139.6,
133.6, 133.1, 132.3, 125.8, 123.4, 106.4; IR νmax 3058, 3039, 3016,
1801, 1746, 1673, 1586, 1508, 1455, 1423, 1401, 1381, 1276, 1247,
1198, 1083, 1063, 942, 924, 902, 832, 765, 750, 729, 711, 692, 636,
580, 544, 519, 490, 459, 434, 423, 406 cm-1; HRMS (EI) m/z [M]+
calcd for C14H679Br81BrI2 587.6900, found 587.6878.
1.00 eq.) 6-H2-Br2 and 628 mg (2.77 mmol, 1.10 eq.) DDQ were
dissolved in 30.0 mL of toluene and refluxed for 4 h. The completion
of the reaction was checked by GCMS. After the solvent was removed
the remaining solid was washed with MeOH. Crystallization from
boiling THF afforded 717 mg (2.13 mmol, 85%) of 8-H2-Br2 as a
pale yellow solid. Mp dec. >230 °C; 1H NMR (pyr-d5, 500 MHz,
373 K) δ 8.42 (s, 2 H), 8.38 (s, 2 H), 8.03-8.04 (m, 2 H), 7.51-7.53 (m,
2 H); 13C{1H} NMR (pyr-d5, 126 MHz, 373 K) δ 133.4, 131.9, 129.2,
127.3, 126.6, 122.2; IR νmax 3057, 2046, 2017, 1939, 1806, 1708,
1605, 1557, 1522, 1462, 1427, 1412, 1282, 1257, 1164, 1133, 1119,
1089, 961, 938, 903, 871, 857, 830, 744, 718, 636, 487, 472, 462,
428, 416 cm-1; HRMS (EI): m/z [M]+ calcd for C14H879Br81Br
335.8967, found 335.8970.
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2,3,6,7-Tetrachloroanthracene (8-Cl2-Cl2). To
a solution of
2,3-Dichloroanthracene (8-H2-Cl2). 50.0 mg (201 µmol, 1.00 eq.)
6-H2-Cl2 and 50.1 mg (221 µmol, 1.10 eq.) DDQ were dissolved in
3 mL of toluene and refluxed for 4 h. The completion of the reaction
was monitored by GCMS. After the solvent was removed the
remaining solid was washed with MeOH. Crystallization from
boiling THF afforded 39.8 mg (161 µmol, 80%) of 8-H2-Cl2 as a pale
470 mg (1.48 mmol, 1.00 eq) 6-Cl2-Cl2 in 14.0 mL toluene 403 mg
DDQ (1.77 mmol, 1.20 eq.) was added and the reaction mixture was
refluxed for 1 h. Purification by recrystallization in boiling toluene
afforded 308 mg (0.97 mmol, 66%) 8-Cl2-Cl2 as a pale yellow solid.
Mp 312 – 316 °C; 1H NMR (Pyr-d5, 500 MHz, 300 K) δ 8,35 (s, 2 H),
8,23 (s, 4 H); 13C{1H} NMR (Pyr-d5, 151 MHz, 300 K) δ 131,6, 131,2,
130,0, 126.0; IR νmax 1604, 1455, 1419, 1399, 1279, 1135, 1110,
1067, 974, 955, 903, 867, 855, 830, 791, 661, 568, 555, 486, 466,
445, 423, 401 cm-1; HRMS (EI) m/z [M]+ calcd for C14H6Cl4 315.9189,
found 315.9175; Anal. calcd for C14H6Cl4: C, 53.21; H, 1.91. Found: C,
53.58; H, 2.27.
2,3-Dichloro-6,7-diiodoanthracene (8-Cl2-I2). To a solution of
662 mg (1.32 mmol, 1.00 eq) 6-Cl2-I2 in 20.0 mL toluene 359 mg
(1.59 mmol, 1.20 eq.) DDQ was added and the reaction mixture was
refluxed for 1 h. Purification by recrystallization in toluene afforded
400 mg (0.80 mmol, 61%) 8-Cl2-I2 as a pale yellow solid. Mp 283 –
285 °C; 1H NMR (Pyr-d5, 600 MHz, 300 K) δ 8.72 (s, 2 H), 8.27 (s, 2
H), 8.21 (s, 2 H); 13C{1H} NMR (Pyr-d5, 151 MHz, 300 K) δ 139.4,
133.0, 131.5, 131.1, 130.1, 125.8, 106.5; IR νmax 2962, 1806, 1746,
1682, 1594, 1556, 1538, 1422, 1397, 1386, 1278, 1259, 1087, 1060,
1016, 972, 939, 849, 834, 795, 770, 754, 738, 699, 658, 615, 576,
490, 469, 439, 412 cm-1; HRMS (EI) m/z [M]+ calcd for C14H6Cl2I2
497.7930, found 497.7915; Anal. calcd for C14H6Cl2I2: C, 33.70; H,
1.21. Found: C, 33.82; H, 1.57.
2,3-Dibromo-6,7-bis(phenylethynyl)-9,10-dihydroanthracene
(9). In a flame dried flask 700 mg (1.19 mmol, 1.00 eq.) 6-Br2-I2,
58.3 mg (83.1 µmol, 0.07 eq.) Pd(PPh3)2Cl2) and 27.1 mg (142 µmol,
0.12 eq.) CuI were dissolved in 10 ml THF and 2.50 ml
diisopropylamine was added. While stirring under nitrogen gas
stream 326 µl (2.97 mmol, 2.50 eq.) ethynyl benzene was added.
After the addition, the reaction mixture was refluxed for 16 h. The
solvent was removed and purification by column chromatography
(SiO2; PE:Et2O 19:1) afforded 587 mg (1.09 mmol, 92%) of 9 as a
pale yellow solid. Mp 189 - 190 °C; 1H NMR (CD2Cl2, 500 MHz,
300 K) δ 7.57-7.59 (m, 6 H), 7.50 (s, 2H), 7.37-7.38 (m, 6 H), 3.89 (s,
4 H); 13C{1H} NMR (CD2Cl2, 126 MHz, 300 K) δ 137.7, 136.6, 132.8,
132.1, 131.3, 129.1, 129.0, 124.2, 123.7, 122.4, 93.6, 88.6, 35.4; IR
νmax 3049, 2921, 2809, 2359, 2207, 1946, 1712, 1596, 1570, 1548,
1494, 1464, 1441, 1416, 1366, 1314, 1261, 1202, 1156, 1116, 1067,
1024, 936, 907, 846, 835, 750, 684, 638, 587, 530, 502, 484, 428,
409 cm-1; HRMS (DART) m/z [M+H]+ calcd for C30H1979Br81Br
538.9828, found 538.9823.
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yellow solid. Mp 246 - 247°C; H NMR (pyr-d5, 500 MHz, 300 K) δ
8.42 (s, 2H), 8.23 (s, 2H), 8.04-8.06 (m, 2H), 7.52-7.54 ppm (m, 2H);
13C{1H} NMR (pyr-d5, 126 MHz, 373 K) δ 133.4, 131.2, 130.3, 130.0,
129.1, 127.3, 126.6; IR νmax 3060, 2363, 1612, 1558, 1520, 1421,
1284, 1167, 1111, 975, 904, 748, 659, 541, 476, 440, 414 cm-1;
HRMS (EI) m/z [M]+ calcd for C14H8Cl2 245.9998, found 245.9989.
2,3-Diiodoanthracene (8-H2-I2). 300 mg (694 µmol, 1.00 eq.) 6-
H2-I2 and 173 mg (764 µmol, 1.10 eq.) DDQ were dissolved in 10 mL
of toluene and refluxed for 4 h. The completion of the reaction was
monitored by GCMS. After the solvent was removed the remaining
solid was washed with MeOH. Crystallization from boiling THF
afforded 239 mg (555 µmol, 80%) of 8-H2-I2 as a pale yellow solid.
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Mp 255 - 256 °C; H NMR (pyr-d5, 500 MHz, 373 K) δ 8.77 (s, 2H),
8.36 (s, 2H), 8.03-8.05 (m, 2H), 7.50-7.52 (m, 2H); 13C{1H} NMR (pyr-
d5, 126 MHz, 373 K) δ 139.6, 133.4, 132.7, 129.2, 127.3, 126.4,
104.7; IR νmax 3049, 1802, 1722, 1698, 1622, 1602, 1545, 1519, 1460,
1422, 1401, 1331, 1281, 1165, 1119, 1064, 957, 922, 900, 854, 741,
704, 630, 522, 481, 468, 433, 419, 405 cm-1; HRMS (EI) m/z [M]+
calcd for C14H8I2 429.8710, found 429.8722; Anal. calcd for C14H8I2:
C, 39.10; H, 1.88. Found: C, 39.40; H, 2.08.
2,3,6,7-Tetrabromoanthracene (8-Br2-Br2). 140 mg (282 µmol,
1.00 eq.) 6-Br2-Br2 and 70.5 mg (311 µmol, 1.10 eq.) DDQ were
dissolved in 10 mL of toluene and refluxed for 4 h. The completion
of the reaction was monitored by GCMS. After the solvent was
reduced the remaining solid was washed with MeOH/EtOH.
Crystallization from boiling toluene afforded 114 mg (231 µmol,
82%) of 8-Br2-Br2 as a pale yellow solid. Mp 344 - 345 °C; 1H NMR
(pyr-d5, 500 MHz, 373 K) δ 8.42 (s, 4 H), 8.31 ppm (s, 2 H); 13C{1H}
NMR (pyr-d5, 126 MHz, 373 K) δ 133.5, 132.4, 126.1, 123.4; IR νmax
3066, 3019, 2362, 2337, 1803, 1747, 1675, 1594, 1514, 1442, 1403,
1389, 1279, 1213, 1082, 942, 922, 903, 875, 844, 834, 792, 763, 730,
711, 693, 641, 592, 508, 462, 422 cm-1; HRMS (EI) m/z [M]+ calcd for
C14H679Br281Br2 493.7157, found 493.7144.
2,3-Dibromo-6,7-dichloroanthracene (8-Br2-Cl2).
150 mg
(369 µmol, 1.00 eq.) 6-Br2-Cl2 and 92.0 mg (405 µmol, 1.10 eq.)
DDQ were dissolved in 10 mL of toluene and refluxed for 4 h. The
completion of the reaction was monitored by GCMS. After the
solvent was reduced the remaining solid was washed with
MeOH/EtOH. Crystallization from boiling toluene afforded 113 mg
(279 µmol, 76%) of 8-Br2-Cl2 as a pale yellow solid. Mp 327 - 328 °C;
1H NMR (pyr-d5, 500 MHz, 373 K) δ 8.43 (s, 2 H), 8.32 (s, 2 H), 8.22
(s, 2 H); 13C{1H} NMR (pyr-d5, 126 MHz, 373 K) δ 133.5, 132.4, 131.7,
131.4, 130.1, 126.0, 123.4; IR νmax 3064, 3023, 2358, 2330, 1804,
1747, 1677, 1596, 1518, 1431, 1413, 1394, 1312, 1280, 1259, 1138,
1111, 1087, 977, 947, 931, 902, 874, 851, 835, 778, 731, 712, 693,
657, 634, 593, 493, 463, 443, 430 cm-1; HRMS (EI) m/z [M]+ calcd for
2,2'-(6,7-Bis(phenylethynyl)-9,10-dihydroanthracene-2,3-
diyl)dithiophene (10). In a flame dried flask, a mixture of 200 mg
(372 µmol, 1.00 eq.) 9, 143 mg (1.11 mmol, 3.00 eq.) 2-
thienylboronic acid, 42.9 mg (37.2 µmol, 0.10 eq.) Pd(PPh3)4,
98.5 mg (929 µmol, 2.50 eq.) Na2CO3, 6 ml H2O and 18 ml THF were
degassed with nitrogen for 5 minutes and stirred at 80 °C for 3 days.
The solvent was removed and purification by column
chromatography (SiO2; PE:Et2O 19:1) afforded 172 mg (316 µmol,
85%) of 10 as a pale yellow solid. Mp 216 - 217 °C; 1H NMR (CD2Cl2,
500 MHz, 300 K) δ 7.58-7.60 (m, 4 H), 7.55 (s, 2 H), 7.46 (s, 2 H),
7.36-7.39 (m, 6 H), 7.28-7.30 (m, 2 H), 6.96-6.98 (m, 2 H), 6.90-6.91
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