Synthesis of p-Quinones and Protected p-Dihydroquinones
J . Org. Chem., Vol. 62, No. 16, 1997 5533
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(hexane-AcOEt); IR 3500-2500 br, 1659, 1619 cm-1; 1H NMR
δ 1.22 (t, J ) 7.5 Hz, 3H), 1.42 (t, J ) 7.5 Hz, 3H), 4.36 (q, J
) 7.5 Hz, 2H), 4.46 (q, J ) 7.5 Hz, 2H), 7.05-7.15 (m, 5H),
1080 cm-1; H NMR δ 2.15 (s, 6H), 2.36 (s, 6H), 5.25 (s, 1H),
7.06-7.16 (m, 2H), 7.33-7.40 (m, 2H). Anal. Calcd for C16
H17FO2S: C, 65.73; H, 5.86. Found: C, 65.70; H, 5.87.
-
7.57-7.64 (m, 2H), 8.35-8.51 (m, 2H). Anal. Calcd for C22
-
2-(3-Hydr oxypr opyl)-3,5,6-tr im eth yl-4-(ph en ylsu lfin yl)-
p h en ol (3m ): quant. from the corresponding 6l; white crystals;
mp 146-148 °C (CH2Cl2-hexane); IR 3500-3000 br, 1555,
1080 cm-1; 1H NMR δ 1.76-1.82 (m, 2H), 2.15 (s, 3H), 2.34 (s,
3H), 2.37 (s, 3H), 2.77 (t, J ) 6.5 Hz, 2H), 3.45 (br s, 1H), 3.53-
3.58 (m, 2H), 7.35-7.43 (m, 5H), 8.28 (s, 1H). Anal. Calcd
for C18H22O3S: C, 67.89; H, 6.96. Found: C, 67.57; H, 6.95.
Rea ction of 4i w ith P h MgBr . Under a nitrogen atmo-
sphere, to a solution of 4i (179 mg, 1.0 mmol) in dry THF (10
mL) was added PhMgBr (3.0 M Et2O solution, 1.0 mL, 3.0
mmol) slowly at -50 °C, and the stirring was continued for 4
h. The reaction mixture was quenched with saturated aqueous
NH4Cl at the same temperature and extracted with AcOEt.
The organic layer was washed with brine, dried with Na2SO4,
and concentrated in vacuo. The residue was purified by
column chromatography (CH2Cl2 f CH2Cl2-MeOH 50:1 f
CH2Cl2-MeOH 20:1) to give 2i (120 mg, 52%) and 8i (64 mg,
42%). 8i: pale yellow crystals; mp 187-189 °C (benzene); IR
3333, 1586, 1306, 1161 cm-1; 1H NMR δ 2.20 (s, 12H), 4.92 (s,
2H), 6.50 (s, 4H). Anal. Calcd for C16H18O2S2: C, 62.71; H,
5.92; S, 20.92. Found: C, 62.62; H, 5.85; S, 20.82.
H20O5S: C, 66.65; H, 5.08; S, 8.09. Found: C, 66.54; H, 5.10;
S, 8.04.
The product 2o (100 mg, 0.25 mmol) was treated with
m-CPBA (56 mg, 80% purity, 0.25 mmol) as shown above, and
the crude product was purified by column chromatography
(hexane-AcOEt 3:1) to give 3o (83 mg, 80%) as yellow
crystals: mp 161-164 °C (CH2Cl2-hexane); IR 1734, 1663,
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1619, 1580, 1084, 1049 cm-1; H NMR δ 1.43 (t, J ) 7.0 Hz,
3H), 1.45 (t, J ) 7.0 Hz, 3H), 4.42-4.54 (m, 4H), 7.31-7.74
(m, 7H), 8.42-8.45 (m, 1H), 8.57-8.60 (m, 1H), 13.12 (s, 1H).
Anal. Calcd for C22H20O6S: C, 64.06; H, 4.89; S, 7.77.
Found: C, 63.83; H, 4.93; S, 7.80.
4-(ter t-Bu tylsu lfin yl)-2,3,5,6-tetr a m eth ylp h en ol (3g):
65% from the corresponding 4; white crystals; mp 158-159
°C (CH2Cl2); IR 3300-2900 br, 1555, 1005; 1H NMR δ 1.26 (s,
9H), 2.14 (s, 3H), 2.16 (s, 3H), 2.36 (s, 3H), 2.66 (s, 3H), 5.19
(s, 1H). Anal. Calcd for C14H22O2S: C, 66.10; H, 8.72; S, 12.60.
Found: C, 66.03; H, 8.61; S, 12.55.
2,3,5-Tr im eth yl-4-(p h en ylsu lfin yl)p h en ol (3j): 63% from
the corresponding 4; white crystals; mp 129-130 °C (CH2Cl2-
hexane); IR 3300-2900 br, 1582 cm-1; 1H NMR δ 2.10 (s, 3H),
2.33 (s, 3H), 2.37 (s, 3H), 5.76 (s, 1H), 6.49 (s, 1H), 7.38-7.44
(m, 5H). Anal. Calcd for C15H16O2S: C, 69.20; H, 6.19.
Found: C, 68.97; H, 6.23.
2,3,5,6-Tetr a m eth yl-4-(p h en ylsu lfin yl)p h en yl Aceta te
(6a ). 6a was prepared by the acetylation (Ac2O, pyridine) of
3a . 6a : quant.; white crystals; mp 164-165 °C (hexane); IR
1755, 1200, 1080, 1044 cm-1; H NMR δ 2.05 (s, 6H), 2.37 (s,
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6H), 2.40 (s, 3H), 7.42 (brs, 5H). Anal. Calcd for C18H20O3S:
C, 68.33; H, 6.37; S, 10.13. Found: C, 68.34; H, 6.33; S, 10.24.
Meth yl 2,3,5,6-Tetr a m eth yl-4-(p h en ylsu lfin yl)p h en yl
Eth er (6b). 6b was prepared by the methylation (MeI and
K2CO3) of 3a . 6b: quant.; white crystals; mp 133-135 °C
2-Acetyl-3,5,6-tr im eth yl-4-(p h en ylsu lfin yl)p h en ol (3k ):
45% from the corresponding 4; white crystals; mp 129-131
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°C (CH2Cl2-hexane); IR 3300-2750 br, 1698, 1620 cm-1; H
NMR δ 2.15 (s, 3H), 2.39 (s, 3H), 2.61 (s, 3H), 2.67 (s, 3H),
7.36-7.46 (m, 5H), 11.87 (s, 1H). Anal. Calcd for C17H18O3S:
C, 67.52; H, 6.00; S, 10.60. Found: C, 67.24; H, 5.97; S, 10.54.
2-Allyl-3,5,6-tr im eth yl-4-(ph en ylsu lfin yl)ph en ol (3l): 70%
from the corresponding 4; white crystals; mp 99-100 °C (CH2-
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(hexane); IR 1100, 1082, 1044 cm-1; H NMR δ 2.19 (s, 6H),
2.37 (s, 6H), 3.66 (s, 3H), 7.41 (brs, 5H). Anal. Calcd for
C17H20O2S: C, 70.79; H, 6.99; S, 11.12. Found: C, 70.68; H,
7.06; S, 10.94.
Cl2-hexane); IR 3400-2900 br, 1636, 1582, 1557, 1080 cm-1
;
1H NMR δ 2.14 (s, 3H), 2.36 (s, 3H), 2.39 (s, 3H), 3.42 (d, J )
5.5 Hz, 2H), 4.99 (dd, J ) 16.0, 1.5 Hz, 1H), 5.09 (dd, J ) 10.5,
1.5 Hz, 1H), 5.92 (ddt, J ) 16.0, 10.5, 5.5 Hz, 1H), 7.33-7.46
(m, 5H). Anal. Calcd for C18H20O2S: C, 71.97; H, 6.71; S,
10.67. Found: C, 71.91; H, 6.75; S, 10.56.
ter t-Bu tyld im eth ylsilyl 2,3,5,6-Tetr a m eth yl-4-(p h en yl-
su lfin yl)ph en yl Eth er (6c). Typical P r ocedu r e for P r epa-
r a tion of th e Silyl Eth er s 6c-f,h ,j,p fr om 3. Under a
nitrogen atmosphere, imidazole (0.26 g, 3.8 mmol) and tBuMe2-
SiCl (0.41 g, 2.7 mmol) were added to an ice-cooled solution of
3a (0.50 g, 1.8 mmol) in dry DMF (6 mL), and the reaction
mixture was stirred at room temperature for 30 h. Ether (30
mL) was added, and the whole mixture was washed with water
(30 mL × 2), dried with MgSO4, and concentrated in vacuo.
The residue was purified by column chromatography (hexane-
AcOEt 5:1) to give 6c (0.69 g, 97%) as white crystals: mp 125-
2-(Eth oxyca r bon yl)-3-m eth yl-4-(p h en ylsu lfin yl)n a p h -
th ol (3n ): 46% from the corresponding 4; white crystals; mp
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161-164 °C (CH2Cl2-hexane); IR 1736, 1669, 1597 cm-1; H
NMR δ 1.48 (t, J ) 7.0 Hz, 3H), 2.99 (s, 3H), 4.53 (q, J ) 7.0
Hz, 2H), 7.31-7.54 (m, 7H), 8.43 (d, J ) 7.5 Hz, 1H), 8.55 (d,
J ) 8.5 Hz, 1H), 13.05 (s, 1H). Anal. Calcd for C20H18O4S:
C, 67.78; H, 5.12; S, 9.05. Found: C, 67.68; H, 5.15; S, 9.05.
2-(N,N-Diet h ylca r b a m oyl)-3-m et h yl-4-(p h en ylsu lfin -
yl)n a p h th ol (3p ): 77% from the corresponding 4; white
crystals mp 154-156 °C (CH2Cl2-hexane); IR 1617, 1605,
1561, 1082, 1042 cm-1; 1H NMR δ 1.09-1.28 (m, 6H), 2.64 (s,
3H), 3.20-3.80 (s, 4H), 7.29-7.46 (m, 7H), 8.12 (d, J ) 8.0
Hz, 1H), 8.37 (brs, 1H), 8.46 (d, J ) 8.0 Hz, 1H); HRMS calcd
for C22H23NO3S 381.1398, found 381.1386.
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127 °C (hexane); IR 1551, 1109, 1082, 1046 cm-1; H NMR δ
0.14 (s, 6H), 1.05 (s, 9H), 2.10 (s, 6H), 2.34 (s, 6H), 7.40 (brs,
5H). Anal. Calcd for C22H32O2SSi: C, 67.99; H, 8.30; S, 8.25.
Found: C, 67.96; H, 8.20; S, 8.17.
Tr iisopr opylsilyl 2,3,5,6-tetr am eth yl-4-(ph en ylsu lfin yl)-
p h en yl eth er (6d ): 70% from 3a ; white crystals; mp 148-
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150 °C (hexane); IR 1551, 1300, 1115, 1044 cm-1; H NMR δ
1.10 (d, J ) 6.0 Hz, 18H), 1.11 (s, 9H), 1.17-1.40 (m, 3H),
2.14 (s, 6H), 2.34 (s, 6H), 7.35-7.40 (m, 5H). Anal. Calcd for
C25H38O2SSi: C, 69.71; H, 8.89; S, 7.44. Found: C, 69.56; H,
8.86; S, 7.33.
2,3-Bis(N,N-dieth ylcar bam oyl)-4-(ph en ylsu lfin yl)n aph -
th ol (3q): 41% from the corresponding 4; white crystals; mp
96-98 °C (hexane-CH2Cl2); IR 3200-2400 br, 1636, 1601,
1559, 1082, 1046 cm-1; 1H NMR δ 1.06-1.36 (m, 12H), 3.15-
3.92 (m, 8H), 7.27-7.43 (m, 5H), 7.84 (d, J ) 7.0 Hz, 2H), 8.07
(d, J ) 8.0 Hz, 1H), 8.53 (d, J ) 8.0 Hz, 1H); HRMS calcd for
C26H30N2O4S 466.1926, found 466.1928.
4-[(4-F lu or op h en yl)su lfin yl]-2,3,5,6-t et r a m et h ylp h e-
n ol (3e). Typ ica l P r oced u r e for Desilyla tion of 6. To an
ice-cooled solution of 6g (45 mg, 0.11 mmol) (whose preparation
is shown below) in THF (2.5 mL) and H2O (0.5 mL) was added
Bu4NF (1.0 M THF solution, 0.050 mL, 0.050 mmol), and the
reaction mixture was stirred for 1 h. The reaction mixture
was poured into saturated aqueous NH4Cl and extracted with
CH2Cl2. The organic layer was separated, and the aqueous
layer was extracted with CH2Cl2. The combined organic layer
was washed with brine, dried with Na2SO4, and concentrated
in vacuo. The residue was purified by preparative TLC (CH2-
Cl2-MeOH 50:1) to give 3e (31 mg, 98%) as white crystals:
mp 131-133 °C (CH2Cl2-hexane); IR 3700-3000 br, 1588,
ter t-Bu tyld ip h en ylsilyl 2,3,5,6-tetr a m eth yl-4-(p h en yl-
su lfin yl)p h en yl eth er (6e): 94% from 3a ; white crystals; mp
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161-163 °C (hexane); IR 1298, 1113, 1044 cm-1; H NMR δ
1.12 (s, 9H), 1.90 (s, 6H), 2.25 (s, 6H), 7.30-7.46 (m, 11H),
7.62-7.72 (m, 4H). Anal. Calcd for C32H36O2SSi: C, 74.95;
H, 7.08; S, 6.25. Found: C, 75.16; H, 7.24; S, 6.38.
ter t-Bu tyld im eth ylsilyl 4-[(4-m eth oxyp h en yl)su lfin yl]-
2,3,5,6-tetr a m eth ylp h en yl eth er (6f): quant. from 3b; white
crystals; mp 142-144 °C (hexane); IR 1593, 1495, 1109, 1084,
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1044 cm-1; H NMR δ 0.14 (s, 6H), 1.05 (s, 9H), 2.10 (s, 6H),
2.35 (s, 6H), 3.83 (s, 3H), 6.93 (d, J ) 8.5 Hz, 2H), 7.30 (d, J
) 8.5 Hz, 2H). Anal. Calcd for C23H34O3SSi: C, 65.98; H, 8.19;
S, 7.66. Found: C, 65.80; H, 8.17; S, 7.63.
ter t-Bu tyld im eth ylsilyl 2,3,5,6-tetr a m eth yl-4-[(4-n itr o-
p h en yl)su lfin yl]p h en yl eth er (6h ): 41% from 3h ; pale
yellow crystals; mp 136-138 °C (hexane); IR 1526, 1347, 1109,
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1011 cm-1; H NMR δ 0.15 (s, 6H), 1.05 (s, 9H), 2.11 (s, 6H),