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M. Periasamy et al.
PAPER
13C NMR: δ = 147.0, 142.5, 133.7, 128.9, 128.7, 128.0, 126.8,
126.1, 122.7, 111.1, 80.7, 44.1, 12.6.
13C NMR: δ = 140.2, 137.7, 136.8, 132.4, 129.9, 129.2, 128.4,
128.3, 127.8, 127.1, 123.8, 21.4.
MS (EI): m/z = 507 [M + H]+.
MS (EI): m/z = 333 [[M + H]+.
Anal. Calcd for C34H38N2O2: C, 80.60; H, 7.56; N, 5.53. Found: C,
80.48; H, 7.49; N, 5.65.
Anal. Calcd for C26H20: C, 93.94; H, 6.06. Found: C, 93.76; H, 6.12.
1,2-Bis(4-methoxyphenyl)acenaphthylene (2c)
Red solid; yield: 320 mg (88%); mp 106–108 °C (Lit.22a 106–
107 °C).
9,10-Diaryl-9,10-dihydroanthracene-9,10-diols 6a and 6c; Gen-
eral Procedure
Diols 6a and 6c were synthesized via reaction of the Grignard re-
agent prepared from the appropriate aryl bromide (8 mmol) and
magnesium turnings (192 mg, 8 mmol) in THF (30 mL) with 9,10-
anthraquinone (416 mg, 2 mmol) in 1,4-dioxane (60 mL).
IR (KBr): 3040, 2955, 1541, 1491 cm–1.
1H NMR: δ = 7.84 (d, J = 8.0 Hz, 2 H), 7.71 (d, J = 6.8 Hz, 2 H),
7.60–7.56 (m, 2 H), 7.39 (d, J = 8.8 Hz, 4 H), 6.92 (d, J = 8.8 Hz, 4
H), 3.85 (s, 6 H).
13C NMR: δ = 158.7, 140.3, 136.9, 131.2, 128.3, 128.2, 127.8,
127.7, 127.0, 123.6, 113.9, 55.2.
9,10-Diphenyl-9,10-dihydroanthracene-9,10-diol (6a)
White solid; yield: 328 mg (45%); mp 242–244 °C.
IR (KBr): 3576 cm–1.
1H NMR: δ = 7.51–7.23 (m, 18 H), 2.69 (s, 2 H).
13C NMR: δ = 148.1, 140.6, 128.5, 128.4, 128.1, 126.8, 126.6, 74.4.
MS (EI): m/z = 365 [M + H]+.
MS (EI): m/z = 365 [M + H]+.
1,2-Bis[4-(trifluoromethyl)phenyl]acenaphthylene (2d)
Yellow solid; yield: 374 mg (85%); mp 166–168 °C.
IR (KBr): 3057, 1614, 1433, 1323 cm–1.
Anal. Calcd for C26H20O2: C, 85.69; H, 5.53. Found: C, 85.52; H,
5.48.
1H NMR: δ = 7.95 (d, J = 8 Hz, 2 H), 7.76 (d, J = 6.8 Hz, 2 H),
7.67–7.65 (m, 6 H), 7.54 (d, J = 8 Hz, 4 H).
13C NMR: δ = 138.9, 138.5, 137.8, 130.2, 129.4 (q, J = 32 Hz),
128.6, 128.1, 128.0, 125.6, 125.5, 124.4, 124.3 (q, J = 271 Hz).
MS (EI): m/z = 441 [M + H]+.
9,10-Bis[4-(diethylamino)phenyl]-9,10-dihydroanthracene-
9,10-diol (6c)
White solid; yield: 556 mg (55%); mp 222–224 °C.
IR (KBr): 3553, 3427 cm–1.
Anal. Calcd for C26H14F6: C, 70.91; H, 3.20. Found: C, 70.85; H,
3.28.
1H NMR: δ = 7.52–7.49 (m, 4 H), 7.29–7.27 (m, 4 H), 7.21 (d, J = 8
Hz, 4 H), 6.61 (d, J = 8 Hz, 4 H), 3.34 (q, J = 7.2 Hz, 8 H), 2.59 (s,
2 H), 1.17 (t, J = 7.2 Hz, 12 H).
13C NMR: δ = 146.6, 141.7, 134.1, 127.9, 127.8, 127.7, 110.9, 74.5,
44.2, 12.6.
1,2-Bis[3,5-bis(trifluoromethyl)phenyl]acenaphthylene (2e)
Yellow solid; yield: 478 mg (83%); mp 160–162 °C.
IR (KBr): 3057, 1618, 1539 cm–1.
MS (EI): m/z = 507 [M + H]+.
1H NMR: δ = 8.02 (d, J = 8.4 Hz, 2 H), 7.90–7.70 (m, 10 H).
Anal. Calcd for C34H38N2O2: C, 80.60; H, 7.56; N, 5.53. Found: C,
80.68; H, 7.51; N, 5.75.
13C NMR: δ = 137.7, 136.9, 136.4, 132.3 (q, J = 33 Hz), 129.9,
129.0, 128.8, 128.3, 127.8, 124.8, 123.0 (q, J = 271 Hz), 121.4.
MS (EI): m/z = 577 [M + H]+.
1,2-Diphenylacenaphthylene (2a); Typical Procedure
To a soln of diol 1a (338 mg, 1 mmol) and Et3N (0.56 mL, 4 mmol)
in CH2Cl2 (15 mL), TiCl4 (0.44 mL of 1:1 TiCl4–CH2Cl2 soln, 2
mmol) in CH2Cl2 (5 mL) was added dropwise over 5 min at 0 °C un-
der N2 atmosphere. The mixture was stirred for 0.5 h at 0–25 °C,
then the reaction was quenched with sat. NH4Cl soln (5 mL). The
organic layer was separated and the aqueous layer was extracted
with CH2Cl2 (2 × 25 mL). The combined organic extract was
washed with brine soln (10 mL) and dried over anhyd Na2SO4. The
solvent was removed and the residue was chromatographed on a sil-
ica gel column (hexane–EtOAc, 97:3) to give 2a.
Anal. Calcd for C28H12F12: C, 58.36; H, 2.10. Found: C, 58.45; H,
2.16.
1,2-Bis[4-(dimethylamino)phenyl]acenaphthylene (2f)
Dark red solid; yield: 312 mg (80%); mp 206–208 °C.
IR (KBr): 3040, 2922, 1606 cm–1.
1H NMR: δ = 7.81 (d, J = 8 Hz, 2 H), 7.76 (d, J = 8 Hz, 2 H), 7.60–
7.56 (m, 2 H), 7.46–7.43 (m, 4 H), 6.79 (d, J = 8.4 Hz, 4 H), 3.02 (s,
12 H).
13C NMR: δ = 149.3, 141.0, 136.4, 130.9, 128.6, 128.3, 127.7,
126.5, 123.9, 123.2, 112.3, 40.5.
Orange solid; yield: 274 mg (90%); mp 162–163 °C (Lit.22d 161–
163 °C).
IR (KBr): 3059, 1479, 1427 cm–1.
MS (EI): m/z = 391 [M + H]+.
Anal. Calcd for C28H26N2: C, 86.12; H, 6.71; N, 7.17. Found: C,
86.08; H, 6.65; N, 7.25.
1H NMR: δ = 7.88 (d, J = 8.4 Hz, 2 H), 7.75 (d, J = 7.2 Hz, 2 H),
7.63–7.59 (m, 2 H), 7.47–7.44 (m, 4 H), 7.39–7.29 (m, 6 H).
13C NMR: δ = 139.9, 138.0, 135.2, 130.8, 128.4, 128.2, 128.1,
127.8, 127.3, 127.1, 124.0.
1,2-Bis[4-(diethylamino)phenyl]acenaphthylene (2g)
Dark red semisolid; yield: 392 mg (88%).
IR (KBr): 3038, 2970, 1608 cm–1.
MS (EI): m/z = 305 [M + H]+.
1H NMR: δ = 7.85–7.83 (m, 4 H), 7.65–7.61 (m, 2 H), 7.52–7.49
(m, 4 H), 6.77 (d, J = 8.4 Hz, 4 H), 3.45 (q, J = 6.8 Hz, 8 H), 1.27
(t, J = 6.8 Hz, 12 H).
13C NMR: δ = 146.5, 141.0, 135.9, 131.0, 128.5, 128.1, 127.5,
126.2, 123.0, 122.7, 111.4, 44.2, 12.7.
1,2-Bis(4-methylphenyl)acenaphthylene (2b)
Orange solid; yield: 305 mg (92%); mp 120–122 °C.
IR (KBr): 3036, 2914, 1481, 1431 cm–1.
1H NMR: δ = 7.87 (d, J = 8.4 Hz, 2 H), 7.76 (d, J = 6.8 Hz, 2 H),
7.63–7.59 (m, 2 H), 7.40–7.39 (m, 4 H), 7.23–7.20 (m, 4 H), 2.43
(s, 6 H).
MS (EI): m/z = 447 [M + H]+.
Anal. Calcd for C32H34N2: C, 86.05; H, 7.67; N, 6.27. Found: C,
86.15; H, 7.72; N, 6.37.
Synthesis 2013, 45, 2913–2918
© Georg Thieme Verlag Stuttgart · New York