S. S. Yoon et al.
FULL PAPER
140.1, 137.8, 136.5, 135.5, 134.0, 131.8, 131.0, 130.3, 129.3, 128.5,
128.0, 127.4, 127.2, 126.4, 126.2, 126.1, 126.0, 125.6, 124.0, 123.8,
7.8 Hz, 4 H), 7.18 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 192.1, 148.2, 140.6, 140.4, 140.0, 139.7, 139.4, 134.7,
130.9, 130.7, 130.6, 130.4, 129.6, 128.9, 128.6, 127.9, 127.5, 127.1,
122.7, 120.8, 120.5, 119.5, 56.2, 32.8, 8.7 ppm. FTIR (ATR): ν =
˜
3040, 2965, 2930, 1588, 1492, 1467, 1276, 1032, 882, 799, 776, 752,
126.9 ppm. FTIR (ATR): ν = 3064, 2837, 1698, 1603, 1475, 1208,
˜
696 cmϪ1. MS (FAB+): m/z = 743 [M+]. HRMS (FAB+): calcd. for 1169, 1005, 838, 765, 752, 735, 689 cmϪ1. MS (EI+): m/z = 334
C57H45N [M+] 743.3569; found 743.3569. HPLC (Capcellpak C18
[M+]. HRMS (EI+): calcd. C25H18O [M+] 334.1358; found
334.1359.
MG, 1 mLminϪ1, 85:15 MeOH/EtOAc): tR = 15.21 min (99.31%).
4-(9,9-Diphenyl-9H-fluoren-4-yl)benzaldehyde (7): Compound 7 was
synthesized similarly to compound 5 in a yield of 74%. M.p. 178–
180 °C. H NMR (300 MHz, CDCl3): δ = 10.14 (s, 1 H), 8.02 (d,
J = 8.2 Hz, 3 H), 7.70 (d, J = 8.1 Hz, 3 H), 7.46 (dd, J = 1.2,
7.6 Hz, 2 H), 7.39 (d, J = 7.6 Hz, 3 H), 7.31 (t, J = 7.6 Hz, 3 H),
7.18 (td, J = 1.2, 7.5 Hz, 4 H), 7.02 (td, J = 1.2, 7.6 Hz, 2 H), 6.89
(d, J = 7.5 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 192.2,
152.5, 151.9, 147.7, 146.0, 139.6, 137.0, 136.7, 135.8, 130.2, 130.1,
129.3, 128.4, 127.8, 127.4, 127.2, 126.9, 126.5, 126.2, 123.1,
7-{4-[1Ј-(2Ј,3Ј,4Ј,5Ј-Tetraphenyl)phenyl]styryl}-9,9-diethyl-2-N,N-di-
phenylamino-9H-fluorene (1g): Yield: 26%. M.p. 150–152 °C. H
1
1
NMR (300 MHz, CDCl3): δ = 7.61 (s, 1 H), 7.55 (t, J = 8.4 Hz, 2
H), 7.43–7.40 (m, 2 H), 7.33 (d, J = 8.4 Hz, 2 H), 7.27 (s, 1 H),
7.22 (s, 2 H), 7.17–7.08 (m, 14 H), 7.01 (d, J = 7.2 Hz, 3 H), 6.98–
6.92 (m, 7 H), 6.89–6.84 (m, 7 H), 6.80–6.77 (m, 2 H), 2.00–1.85 (m,
4 H), 0.36 (t, J = 7.2 Hz, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ
= 151.7, 150.5, 148.2, 141.9, 141.3, 141.0, 140.9, 140.5, 140.4, 140.1,
139.4, 136.5, 135.7, 135.6, 131.7, 131.7 131.6, 131.4, 130.4, 130.1,
129.3, 127.8, 127.4, 127.2, 127.1, 126.8, 126.4, 126.0, 125.9, 125.5,
124.0, 123.8, 122.6, 120.6, 120.5, 119.5, 119.4, 56.1, 32.8, 8.7 ppm.
65.2 ppm. FTIR (ATR): ν = 3064, 2837, 1700, 1606, 1490, 1447,
˜
1034, 837, 807, 751, 728, 703, 646 cmϪ1. MS (EI+): m/z = 422 [M+].
HRMS (EI+): calcd. for C32H22O [M+] 422.1671; found 422.1673.
FTIR (ATR): ν = 3024, 2963, 1590, 1492, 1466, 1277, 808, 753,
˜
697 cmϪ1. MS (FAB+): m/z = 871 [M+]. HRMS (FAB+): calcd. for
C67H53N [M+] 871.4178; found 871.4177. HPLC (Capcellpak C18
MG, 1 mLminϪ1, 85:15 MeOH/EtOAc): tR = 9.8 min (99.01%).
4-(9,9-Diphenyl-9H-fluoren-2-yl)benzaldehyde (8): Compound 8 was
synthesized similarly to compound 5 in a yield of 77%. M.p. 218–
1
220 °C. H NMR (300 MHz, CDCl3): δ = 10.02 (s, 1 H), 7.90 (d,
J = 8.2 Hz, 3 H), 7.85 (d, J = 8.2 Hz, 2 H), 7.80 (d, J = 7.5 Hz, 2
H), 7.71–7.67 (m, 5 H), 7.64 (dd, J = 1.5, 8.0 Hz, 2 H), 7.44–7.41
(m, 2 H), 7.38–7.36 (m, 2 H), 7.31 (dd, J = 1.2, 7.5 Hz, 2 H), 7.27
(m, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 192.0, 152.3,
151.8, 147.4, 145.8, 140.9, 139.6, 139.3, 135.3, 130.4, 128.5, 128.3,
128.3, 127.8, 127.1, 127.0, 126.5, 125.3, 120.8, 120.6, 65.8 ppm.
7-[2-(4Ј-Tritylbiphenyl-4-yl)vinyl]-9,9-diethyl-2-N,N-diphenyl-
amino-9H-fluorene (1h): Yield: 48%. M.p. 154–156 °C. 1H NMR
(300 MHz, CDCl3): δ = 7.58 (d, J = 8.8 Hz, 4 H), 7.52 (d, J =
8.2 Hz, 3 H), 7.48–7.44 (m, 3 H), 7.30–7.18 (m, 20 H), 7.11 (d, J
= 8.2 Hz, 7 H), 7.04–7.00 (m, 4 H), 2.07–1.86 (m, 4 H), 0.37 (t, J
= 7.0 Hz, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 151.9, 150.7,
148.3, 147.5, 147.0, 146.3, 141.5, 139.7, 138.2, 136.8, 136.6, 135.8,
131.9, 131.4, 129.6, 129.5, 127.8, 127.4, 127.1, 126.2, 126.1, 124.1,
123.9, 122.8, 120.8, 120.7, 119.6, 119.6, 65.1, 56.3, 33.0, 8.9 ppm.
FTIR (ATR): ν = 3064, 2733, 1701, 1602, 1453, 1409, 1213, 1173,
˜
842, 821, 788, 782, 762, 747, 731, 702, 636 cmϪ1. MS (EI+): m/z =
422 [M+]. HRMS (EI+): calcd. for C32H22O [M+] 422.1671; found
422.1669.
FTIR (KBr): ν = 3028, 2970, 1738, 1593, 1492, 1466, 1443, 964,
˜
743, 699, 669 cmϪ1. MS (FAB+): m/z = 809 [M+]. HRMS (FAB+):
calcd. for C62H51N [M+] 809.4022; found 809.4045. HPLC (Cap-
cellpak C18 MG, 1 mLminϪ1, 85:15 MeOH/EtOAc): tR = 13.3 min
(99.06%).
4-(9,9Ј-Spirobifluorene)benzaldehyde (9): Compound 9 was synthe-
sized similarly to compound 5 in a yield of 80%. M.p. 106–108 °C.
1H NMR (300 MHz, CDCl3): δ = 9.96 (s, 1 H), 7.94 (d, J = 8.0 Hz,
1 H), 7.89–7.85 (m, 3 H), 7.80 (d, J = 8.2 Hz, 2 H), 7.66 (dd, J =
1.6, 8.0 Hz, 1 H), 7.57 (d, J = 8.2 Hz, 2 H) 7.38 (t, J = 7.5 Hz, 3
H), 7.15–7.09 (m, 3 H), 6.99 (d, J = 1.8 Hz, 1 H), 6.76 (t, J =
7.6 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 191.9, 149.9,
149.5, 148.6, 147.0, 142.5, 142.0, 141.1, 139.4, 135.2, 130.2, 128.4,
128.1, 128.0, 127.7, 127.4, 124.2, 123.0, 120.7, 120.4, 120.3,
4-(1,1Ј-Binaphthyl-4-yl)benzaldehyde (5): Toluene (18 mL), EtOH
(8.0 mL), and a solution of Na2CO3 (8.0 mL of a 2.0 m) were added
stepwise to a 100 mL, two-necked, round-bottomed flask contain-
ing 4-bromo(1,1Ј)binaphthyl (600 mg, 1.8 mmol), 4-formylphen-
ylboronic acid (324 mg, 2.16 mmol), and tetrakis(triphenylphos-
phane)palladium(0) (83 mg, 0.072 mmol). After the reaction mix-
ture was heated at 120 °C for 3 h, the mixture was extracted with
ethyl acetate and washed with water. The combined organic layers
were dried with anhydrous MgSO4, filtered, and the solvents were
evaporated to dryness. The crude product was purified by column
chromatography (silica gel, hexane) and recrystallized from
CH2Cl2/EtOH to afford compound 5 (510 mg, 80%). M.p. 186–
66.2 ppm. FTIR (ATR): ν = 3062, 1699, 1602, 1448, 1212, 1170,
˜
888, 841, 753, 731, 637 cmϪ1. MS (EI+): m/z = 420 [M+]. HRMS
(EI+): calcd. for C32H20O [M+] 420.1514; found 420.1514.
3,5-Bis(naphthalen-1-yl)benzaldehyde (10): The reaction described
for the synthesis of 5 was carried out starting with 3,5-dibromo-
benzaldehyde (800 mg, 3.03 mmol) and 1-naphthaleneboronic acid
(1.25 g, 7.28 mmol) to afford compound 10 (1.00 g, 92%). M.p.
1
1
188 °C. H NMR (300 MHz, CDCl3): δ = 10.15 (s, 1 H), 8.06 (d,
142–144 °C. H NMR (300 MHz, CDCl3): δ = 10.17 (s, 1 H) 8.09
J = 8.1 Hz, 2 H), 7.99–7.92 (m, 3 H), 7.78 (d, J = 8.0 Hz, 2 H),
7.61 (t, J = 7.2 Hz, 1 H), 7.58–7.55 (m, 3 H), 7.48 (t, J = 8.0 Hz,
4 H) 7.34–7.29 (m, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
192.1, 147.5, 139.2, 138.8, 135.6, 133.7, 133.4, 133.0, 131.3, 131.1,
129.9, 128.4, 128.2, 128.0, 127.5, 127.3, 126.7, 126.6, 126.5, 126.3,
(d, J = 1.8 Hz, 2 H), 7.96 (s, 1 H), 7.93 (d, J = 1.8 Hz, 2 H), 7.92
(dd, J = 2.1, 4.5 Hz, 3 H), 7.89 (d, J = 1.8 Hz, 1 H), 7.57–7.51 (m,
4 H), 7.49 (t, J = 1.8 Hz, 2 H), 7.48–7.45 (m, 2 H) ppm. 13C NMR
(CDCl3, 125 MHz): δ = 192.3, 142.0, 138.6, 137.7, 136.9, 134.0,
131.5, 130.2, 128.7, 128.6, 127.4, 126.7, 126.2, 125.6 ppm. FTIR
126.1, 125.9, 125.6 ppm. FTIR (ATR): ν = 3046, 1697, 1604, 1562,
˜
(ATR): ν = 3067, 2802, 2726, 1700, 1588, 1379, 1199, 1162, 908,
˜
1512, 1503, 1381, 1210, 1166, 827, 800, 771, 730, 694, 630 cmϪ1
.
802, 776, 711, 638 cmϪ1. MS (EI+): m/z = 358 [M+]. HRMS (EI+):
MS (EI+): m/z = 358 [M+]. HRMS (EI+): calcd. for C27H18O [M+]
calcd. for C27H18O [M+] 358.1358; found 358.1357.
358.1358; found 358.1356.
1-(2Ј,3Ј,4Ј,5Ј-Tetraphenyl)phenyl-4-benzaldehyde (11): n-Butyllith-
ium (Aldrich, 1.27 mL of a 1.6 m solution in hexanes, 2.03 mmol)
was added dropwise over 30 min to a mechanically stirred solution
of 1-(2Ј,3Ј,4Ј,5Ј-tetraphenyl)phenyl-4-bromobenzene (730 mg,
4-(2Ј-p-Terphenyl)benzaldehyde (6): Compound 6 was synthesized
similarly to compound 5 in a yield of 63%. M.p. 124–126 °C. H
NMR (300 MHz, CDCl3): δ = 9.96 (s, 1 H), 7.74 (d, J = 8.1 Hz, 2
1
H), 7.57 (d, J = 7.2 Hz, 2 H), 7.52–7.45 (m, 7 H), 7.37 (q, J = 1.35 mmol) in THF (20 mL) cooled in a dry ice/ethanol bath. After
4796 Eur. J. Org. Chem. 2011, 4788–4798
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