PAPER
Synthesis of 9,10-Diarylanthracene Derivatives
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1H NMR (300 MHz, CDCl3): = 7.15–7.16 (m, 1 H, ArH), 7.24–
7.29 (m, 1 H, ArH), 7.38–7.43 (m, 2 H, ArH), 7.53–7.59 (m, 3 H,
ArH) 7.8 (d, J = 9.0 Hz, 2 H, ArH), 8.5 (d, J = 9.0 Hz, 2 H, ArH).
13C NMR (75.43 MHz, CDCl3): = 124.6, 126.0, 127.0, 127.2,
128.0, 129.4, 129.6, 130.3, 132.7, 138.6.
1H NMR (300 MHz, CDCl3): = 7.16–7.78 (m, 9 H, ArH), 7.78 (d,
J = 9.0 Hz, 2 H, ArH), 8.59 (d, J = 9.0 Hz, 2 H, ArH).
13C NMR (75.43 MHz, CDCl3): = 121.4, 122.2, 123.7, 124.6,
124.7, 124.9, 126.2, 126.5, 127.1, 128.0, 129.2, 130.2, 132.2, 139.4,
140.0, 141.3.
HRMS (EI): m/z calcd for C18H11BrS (337.97, M+): 337.9764;
HRMS (EI): m/z calcd for C22H13BrS (M+): 387.9921; found:
found: 337.9761.
387.9913.
UV (CHCl3): max ( ) = 255 (14451), 381 (7482), 400 nm (7122).
UV (CHCl3): max ( ) = 260 (6676), 382 (895), 402 nm (869).
9-Bromo-10-(thien-3-yl)anthracene (16)
9-(5-Acetyl-2-thienyl)-10-bromoanthracene (19)
A mixture of 3 (400 mg, 01.19 mmol), 3-thienylboronic acid (304
mg, 2.38 mmol), [Pd(PPh3)4] (75 mg, 5.5 mol%), Na2CO3 (2 M, 5
mL) and solvent [THF (20 mL) and toluene (20 mL)] was heated at
85 °C under N2 for 10 h. At the conclusion of the reaction (TLC
monitoring), the mixture was worked up according to the general
procedure. The crude product was purified by a silica gel column
chromatography. Elution of the column with petroleum ether gave
the recovered starting material 3 (190 mg) and the desired cross-
coupling product 16 (210 mg, 90%, based on the recovered starting
material 3) as a yellow crystalline solid; mp 184–186 °C; Rf 0.8 (pe-
troleum ether).
A mixture of 3 (30 mg, 0.09 mmol), 5-acetylthiophene-2-boronic
acid (38 mg, 0.22 mmol), [Pd(PPh3)4] (10 mg, 10 mol%), Na2CO3
(24 mg, 0.23 mmol) in H2O (1 mL) and solvent [THF (3 mL) and
toluene (3 mL)] was heated at 85 °C under N2 for 18 h. At the con-
clusion of the reaction (TLC monitoring), the mixture was worked
up according to the general procedure. The crude product was puri-
fied by a silica gel column chromatography. Elution of the column
with petroleum ether gave the recovered starting material 3 (18 mg)
and the desired cross-coupling product 19 (9 mg, 61%, based on the
recovered starting material 3) as a semi-solid; Rf 0.6 (20% EtOAc–
petroleum ether).
1H NMR (300 MHz, CDCl3): = 7.14–7.25 (m, 1 H, ArH), 7.25–
7.43 (m, 3 H, Ar-H), 7.56–7.62 (m, 3 H, ArH), 7.76 (dd, J = 9.0,
0.73 Hz, 2 H, ArH), 8.61 (dd, J = 9.0, 0.73 Hz, 2 H, ArH).
13C NMR (75.43 MHz, CDCl3): = 123.0, 125.2, 125.6, 126.9,
127.1, 127.7, 130.1, 130.6, 131.4, 132.6, 137.9.
IR (KBr): 1661 cm–1.
1H NMR (300 MHz, CDCl3): = 2.68 (s, 3 H, thiophene-COCH3),
7.21 (d, J = 3.6 Hz, 1 H, thiophene-H), 7.44–7.49 (m, 2 H, ArH),
7.59–7.64 (m, 2 H, ArH), 7.78 (d, J = 9.1 Hz, 2 H, ArH), 7.89 (d,
J = 3.6 Hz, 1 Hthiophenyl), 8.61 (d, J = 9.1 Hz, 2 H, ArH).
HRMS (EI): m/z calcd for C18H11BrS: 337.9764; found: 337.9761.
HRMS (EI): m/z calcd for C20H13BrO (379.98, M+): 379.9870;
found: 379.9871.
UV (CHCl3): max ( ) = 257 (11465), 380 (7476), 400 nm (6949).
UV (CHCl3): max ( ) = 260 (71106), 382 (892), 400 nm (869).
9-Bromo-10-(fur-2-yl)anthracene (17)
A mixture of 3 (35 mg, 0.10 mmol), 2-furylboronic acid (23 mg,
0.20 mmol), [Pd(PPh3)4] (10 mg, 8 mol%), Na2CO3 (2 M, 0.5 mL)
and solvent [THF (3 mL) and toluene (3 mL)] was heated at 85 °C
under N2 for 9 h. At the conclusion of the reaction (TLC monitor-
ing), the mixture was worked up according to the general procedure.
The crude product was purified by a silica gel column chromato-
graphy. Elution of the column with petroleum ether gave the recov-
ered starting material 3 (7 mg) and the desired cross-coupling
product 17 (11.5 mg, 65%, based on the recovered starting material
3) as a yellow crystalline solid; mp 159–161 °C; Rf 0.35 (petroleum
ether).
1H NMR (300 MHz, CDCl3): = 6.68–6.69 (m, 1 H, furan-H),
6.72–6.74 (m, 1 H, furan-H), 7.45–7.50 (m, 2 H, Ar), 7.58–7.63 (m,
2 H, ArH), 7.76–7.77 (m, 1 H, ArH), 7.88 (d, J = 8.3 Hz, 2 H, ArH),
8.6 (d, J = 8.3 Hz, 2 H, ArH).
13C NMR (75.43 MHz, CDCl3): = 110.8, 112.5, 124.9, 126.2,
126.3, 126.6, 126.9, 127.8, 130.1, 132.1, 142.9, 149.7.
9-(4-Methylphenyl)-10-(thien-2-yl)anthracene (20)
A mixture of 15 (15 mg, 0.04 mmol), 4-methylphenylboronic acid
(11.5 mg, 0.08 mmol), [Pd(PPh3)4] (5 mg, 10 mol%), Na2CO3 (2 M,
0.5 mL) and solvent [THF (2 mL) and toluene (2 mL)] was heated
at 85 °C under N2 for 8 h. At the conclusion of the reaction (TLC
monitoring), the mixture was worked up according to the general
procedure. The crude product was purified by a silica gel column
chromatography. Elution of the column with petroleum ether gave
the desired cross-coupling product 20 (10 mg, 64%) as a white crys-
talline solid; mp 184–186 °C; Rf 0.75 (petroleum ether).
1H NMR (300 MHz, CDCl3): = 2.53 (s, 3 H, ArCH3), 7.17–7.42
(m, 10 H, ArH), 7.62 (dd, J = 5.1, 1.0 Hz, 1 H, ArH), 7.71 (d, J = 8.6
Hz, 2 H, ArH), 7.87 (d, J = 8.6 Hz, 2 H, ArH).
13C NMR (75.43 MHz, CDCl3): = 21.5 (ArCH3) 125.0, 125.5,
126.7, 127.1, 127.2, 129.2, 129.5, 129.9, 131.1, 131.6, 135.7, 137.2,
138.2, 138.7, 139.3.
HRMS (EI): m/z calcd for C25H18S (M+): 350.1129; found:
350.1124.
HRMS (EI): m/z calcd for C18H11BrO (M+): 321.9993; found:
321.9995.
UV (CHCl3): max ( ) = 265 (12562), 378 (9650), 396 nm (9091).
UV (CHCl3): max ( ) = 255 (14558), 382 (6441), 400 nm (6489).
9-(4-Methylphenyl)-10-(thien-3-yl)anthracene (21)
9-Benzo[b]thien-2-yl-10-bromoanthracene (18)
A mixture of 16 (25 mg, 0.07 mmol), 4-methylphenylboronic acid
(20 mg, 0.146 mmol), [Pd(PPh3)4] (8 mg, 9 mol%), Na2CO3 (2 M,
0.5 mL) and solvent [THF (3 mL) and toluene (3 mL)] was heated
at 85 °C under N2 for 11.5 h. At the conclusion of the reaction (TLC
monitoring), the mixture was worked up according to the general
procedure. The crude product was purified by a silica gel column
chromatography. Elution of the column with petroleum ether gave
the desired cross-coupling product 21 (22 mg, 85%) as a white crys-
talline solid; mp 196–197 °C; Rf 0.75 (petroleum ether).
A mixture of 3 (30 mg, 0.09 mmol), benzo[b]thiophene-2-boronic
acid (38 mg, 0.22 mmol), [Pd(PPh3)4] (10 mg, 10 mol%) Na2CO3
(24 mg, 0.23 mmol) in H2O (1 mL) and solvent [THF (3 mL) and
toluene (3 mL)] was heated at 85 °C under N2 for 14 h. At the con-
clusion of the reaction (TLC monitoring), the mixture was worked
up according to the general procedure. The crude product was puri-
fied by a silica gel column chromatography. Elution of the column
with petroleum ether gave the recovered starting material 3 (14 mg)
and the desired cross-coupling product 18 (17 mg, 92%, based on
the recovered starting material 3) as a yellow crystalline solid; mp
228–230 °C; Rf 0.35 (petroleum ether).
1H NMR (300 MHz, CDCl3): = 2.54 (s, 3 H, ArCH3), 7.25–7.43
(m, 10 H, ArH), 7.60 (dd, J = 4.9, 2.9 Hz, 1 H, ArH), 7.70–7.73 (m,
2 H, ArH), 7.78–7.82 (m, 2 H, ArH).
Synthesis 2004, No. 4, 549–557 © Thieme Stuttgart · New York