H. Nakajima et al.
-Methoxy-1-naphthylboroxin (B): To a solution of 1-
bromo-4-methoxynaphthalene (40 mmol) in toluene (60 mL)
and THF (15 mL) at ¹78 °C was slowly added n-BuLi (1.6 M
in hexane, 30 mL, 48 mmol) for the period of 1.5 h. After the
reaction mixture was stirred for another 1 h at ¹78 °C,
B(Oi-Pr)3 (48 mmol) was slowly added for the period of
Bull. Chem. Soc. Jpn. Vol. 84, No. 10 (2011) 1127
4
129.9, 127.9, 126.8, 125.0, 124.8, 124.7, 122.6, 107.9; MS (EI,
28
+
70 eV): m/z 504 (M , 100.0); HRMS (EI, 70 eV): calcd for
+
C H O 504.1725, found m/z 504.1732 (M ).
3
6
24
3
1-Methoxy-8-phenylnaphthalene (10): To a suspension of
8-methoxy-1-naphthylboronic acid (5.5 mmol) in toluene
(15 mL), EtOH (25 mL), water (15 mL), and Na CO (7.5
2
3
3
0 min at the same temperature. The mixture was allowed to
warm to 0 °C. HCl(aq) solution (2 M, 50 mL) and EtOAc
50 mL) was added to the mixture and it was stirred (for ca. 1 h)
mmol) were added and the mixture was stirred for 1 h at room
temperature. Then, the mixture was added to a solution of
bromobenzene (5 mmol) and [Pd(PPh ) ] (0.25 mmol) in
(
3
4
5
until the organic layer became clear. The mixture was extracted
with EtOAc (3 © 30 mL). The combined organic layer was
washed with sat. NaHCO (aq) and brine, dried over MgSO
and evaporated. The residue was washed with hexane and
filtrated to give a white solid (6.4 g, 87%). Mp: 250252 °C; IR
toluene (10 mL) and stirred for 3 h at 90 °C. The mixture
was cooled to 0 °C and water (30 mL) was added. The mixture
was extracted with ethyl acetate (3 © 10 mL). The combined
organic layer was dried over MgSO4 and evaporated. The
residue was purified by column chromatography (hexane).
Further purification was performed by distillation under
reduced pressure to give the product as a colorless liquid
(0.90 g, 78%). Bp: 150 °C/0.2 mmHg; IR (neat): 1577 (aryl),
3
4
¹
1 1
(
(
KBr): 1574 (aryl), 1512 (aryl), 1238 (COC) cm ; H NMR
400 MHz, CDCl ): ¤ 9.30 (d, 1H, J = 8.4 Hz), 8.64 (d, 1H,
3
J = 7.9 Hz), 8.40 (dd, 1H, J = 8.5, 1.0 Hz), 7.68 (ddd, 1H,
J = 8.5, 6.8, 1.6 Hz), 7.56 (ddd, 1H, J = 8.4, 6.8, 1.0 Hz), 7.02
¹1 1
1253 (COC) cm ; H NMR (400 MHz, CDCl ): ¤ 7.81 (d,
3
(
d, 1H, J = 7.9 Hz), 4.12 (s, 3H); 13C NMR (100 MHz, CDCl3):
J = 8.0 Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.46 (t, J = 8.0 Hz,
1H), 7.40 (t, J = 8.0 Hz, 1H), 7.377.28 (m, 5H), 7.27 (d,
J = 8.0 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 3.48 (s, 3H);
¤
5
159.3, 139.0, 138.6, 128.0, 127.2, 125.7, 125.0, 122.3, 103.4,
+
5.6. MS (EI, 70 eV): m/z 552 (M , 100), 158 (86), 143 (30),
1
3
115 (65); HRMS (EI, 70 eV): calcd for C H B O 552.2087,
C NMR (100 MHz, CDCl ): ¤ 156.7, 145.4, 139.0, 135.7,
3
33
27
3
6
+
found m/z 552.2091 (M ). Anal. Calcd for C33H27B3O6: C,
1.80; H, 4.93%. Found: C, 71.52; H, 4.93%.
,3,5-Tris(4-methoxy-1-naphthyl)benzene (5):
129.0, 128.7, 127.6, 126.6, 126.0, 125.7, 125.4, 123.5, 121.2,
+
7
106.2, 55.2; MS (EI, 70 eV): m/z 234 (M , 100), 218 (52);
1
To a
HRMS (EI, 70 eV): calcd for C H O 234.1045, found m/z
1
7
14
+
suspension of 4-methoxy-1-naphthylboroxin (5.2 mmol) in
toluene (10 mL), EtOH (20 mL), water (12 mL), and Na CO
234.1041 (M ). Anal. Calcd for C H O: C, 87.15; H, 6.02%.
17 14
Found: C, 87.10; H, 6.01%.
2
3
(
20 mmol) were added and the mixture was stirred for 1 h at
room temperature. Then, the mixture was added to a solution of
,3,5-tribromobenzene (4.0 mmol) and [Pd(PPh ) ] (0.4 mmol)
1-Methoxy-4-phenylnaphthalene (13): To a suspension of
4-methoxy-1-naphthylboroxin (1.2 mmol) in toluene (5 mL),
EtOH (15 mL), water (9 mL), and Na CO (5.0 mmol) were
1
3
4
5
2
3
in toluene (10 mL) and stirred for 17 h at 90 °C. The mixture
was cooled to 0 °C and water (30 mL) was added. The mixture
was extracted with ethyl acetate (3 © 30 mL). The combined
organic layer was dried over MgSO4 and evaporated. The
residue was purified by flash column chromatography (hexane/
EtOAc, 95:5) to give the product as a white solid (1.56 g, 71%).
added and the mixture was stirred for 1 h at room temperature.
Then, the mixture was added to a solution of bromobenzene
(3.0 mmol) and [Pd(PPh ) ] (0.15 mmol) in toluene (10 mL)
3
4
5
and stirred for 5 h at 90 °C. The mixture was cooled to 0 °C
and water (30 mL) was added. The mixture was extracted with
ethyl acetate (3 © 30 mL). The combined organic layer was
¹
1 1
Mp: 218221 °C; IR (KBr): 1585 (aryl) cm ; H NMR (400
dried over MgSO and evaporated. The residue was purified by
4
MHz, CDCl ): ¤ 8.35 (m, 3H), 8.18 (m, 3H), 7.67 (s, 3H), 7.50
flash column chromatography (hexane/EtOAc, 95:5) to give
the product as a colorless liquid (0.51 g, 71%). Bp: 170 °C/
0.6 mmHg; IR (neat): 1238 (COC) cm ; H NMR (600
3
m, 9H), 6.90 (d, 3H, J = 8.0 Hz), 4.04 (s, 9H); 1 C NMR
3
(
(
¹1
1
100 MHz, CDCl ): ¤ 155.0, 140.7, 132.43, 132.4, 130.6,
3
1
7
27.2, 126.6, 125.8, 125.7, 125.1, 122.2, 103.5, 55.6; MS (EI,
MHz, CDCl ): ¤ 8.34 (m, 1H), 7.86 (m, 1H), 7.49 (ddd,
3
+
0 eV): m/z 546 (M , 100); HRMS (EI, 70 eV): calcd for
J = 7.8, 6.6, 1.2 Hz, 1H), 7.487.46 (m, 4H), 7.44 (ddd,
J = 7.8, 6.6, 1.2 Hz, 1H), 7.40 (m, 1H), 7.33 (d, J = 7.8 Hz,
+
C H O 546.2195, found m/z 546.2191 (M ). Anal. Calcd
for C H O : C, 85.69; H, 5.53%. Found: C, 85.44; H, 5.50%.
39
30
3
13
1H), 6.87 (d, J = 7.8 Hz, 1H), 4.04 (s, 3H); C NMR
3
9
30
3
1
,3,5-Tris(4-hydroxy-1-naphthyl)benzene (4): To a solu-
(100 MHz, CDCl ): ¤ 155.0, 140.9, 132.7, 132.5, 130.3,
3
tion of 1,3,5-tris(4-methoxy-1-naphthyl)benzene (0.56 mmol)
in CH2Cl2 (3 mL), was slowly added BBr3 (1.0 M in CH2Cl2,
128.2, 126.9, 126.8, 126.5, 125.8, 125.7, 125.1, 122.2, 103.4,
+
+
55.6; MS (EI, 70 eV): m/z 234 (M , 100), 219 (M ¹ CH3,
38), 191 (38); HRMS (EI, 70 eV): calcd for C H O 234.1045,
1
.8 mL) at ¹78 °C. The mixture was stirred at ¹78 °C to rt for
h. The mixture was cooled to 0 °C and quenched by water.
1
7
14
+
8
found m/z 234.1043 (M ). Anal. Calcd for C H O: C, 87.15;
1
7
14
The mixture was extracted with ethyl acetate (3 © 10 mL). The
H, 6.02%. Found: C, 86.96; H, 6.01%.
combined organic layer was dried over MgSO and evaporated.
8-(4-Methoxyphenyl)-1-naphthol (14): To a suspension of
4
The residue was purified by flash column chromatography
CsCO (10 mmol), which was predried under reduced pressure
3
(
(
(
(
hexane/EtOAc, 60:40) to give the product as a white solid
for 2 h at room temperature, in DMF (25 mL) were added PdCl2
(0.13 mmol), 1-naphthol (5.0 mmol), and p-iodoanisole (6.0
mmol). The mixture was stirred for 21 h at 110 °C. The
mixture was cooled to 0 °C, and then water was added. The
mixture was extracted with ethyl acetate (3 © 20 mL). The
combined organic layer was washed with water (3 © 20 mL)
0.254 g, 90%). Mp: decomposition 295 °C; IR (KBr): 3533
¹
1
1
5
OH), 1585 cm ; H NMR (400 MHz, DMSO-d6): ¤ 10.35
brs, 3H), 8.23 (dd, J = 8.3, 1.1 Hz, 3H), 8.08 (d, J = 8.5 Hz,
3
H), 7.55 (ddd, J = 8.5, 6.8, 1.1 Hz, 3H), 7.51 (s, 3H), 7.49 (m,
H), 7.47 (d, J = 7.8 Hz, 3H), 6.97 (d, J = 7.8 Hz, 3H);
3
1
3
C NMR (100 MHz, DMSO-d ): ¤ 153.1, 140.6, 131.9, 129.9,
and dried over MgSO . After filtration, the solvent was
6
4