peri-Hydroxy Aromatic Compounds
J . Org. Chem., Vol. 65, No. 1, 2000 93
1780, 1690 cm-1; 1H NMR (CDCl3) δ 8.60 (1H, d, J ) 9.0 Hz);
8.12 (1H, d, J ) 9.0 Hz), 7.66-6.93 (7H, m), 3.37 (2H, dd, J )
6.2, 5.8 Hz), 2.68 (2H, dd, J ) 6.9, 6.2 Hz), 2.57 (3H, s); 2.11-
2.07 (2H, m); 13C NMR (CDCl3) δ 197.4, 169.4, 149.3, 146.4,
138.6, 137.7, 130.4, 129.1, 127.2, 127.0, 126.6, 126.1, 125.2,
123.7, 121.9, 40.2, 29.9, 22.0, 21.2. Anal. Calcd for C22H18O3S:
C, 72.90; H, 5.01; S, 8.85. Found: C, 72.63; H, 5.09; S, 8.87.
129.2, 128.5, 128.0, 127.7, 127.5, 127.4, 127.1, 122.9, 122.3,
61.3, 31.3, 20.7; HRMS calcd for C21H18O4 (M+) 334.1205, found
334.1206.
2-[2-(1,3-Dioxa n -2-yl)eth yl]cycloh exa n on e (4a ). Under
a nitrogen atmosphere, to a solution of cyclohexanone (1.7 mL,
16.4 mmol) in DMF (30 mL) was added LHMDS (1.0 M in
THF, 17.0 mL, 17 mmol) at 0 °C. After being stirred for 30
min, a solution of 2-(2-iodoethyl)-1,3-dioxane (4.25 g, 17.6
mmol) in DMF (20 mL) was added slowly. The reaction
mixture was stirred for 2.5 h, then quenched with aqueous
NH4Cl solution and extracted with Et2O, dried over anhydrous
Na2SO4, and concentrated in vacuo. The residue was purified
by column chromatography (hexane/AcOEt, 3:1) to give 4a
(2.04 g, 59%) as a colorless oil: IR (KBr) 1713, 1705 cm-1; 1H
NMR (CDCl3) δ 4.52 (1H, t, J ) 5.0 Hz), 4.11-4.05 (2H, m),
3.79-3.30 (2H, m), 2.36-1.30 (15H, m); HRMS calcd for
10-Acet oxy-5-m et h oxy-3,4-d ih yd r oa n t h r a cen -1(2H )-
on e (3g). Compound 3g was obtained as white needles in 62%
yield (53 mg) by the reaction of homophthalic anhydride 1c
(57.6 mg, 0.3 mmol) with enone 2b (66 mg, 0.3 mmol) in the
presence of NaH (11.2 mg of 60% in paraffin oil, 0.33 mmol)
in 4 mL of dioxane: mp 127 °C (CH2Cl2/hexane); IR (KBr)
1
1770, 1690 cm-1; H NMR (CDCl3) δ 8.10-8.02 (2H, m); 7.63
(1H, dd, J ) 8.0, 7.0 Hz), 7.52 (1H, m), 3.91 (3H, s), 3.14 (2H,
bs), 2.68 (2H, m), 2.54 (3H, s), 2.15-2.02 (2H, m); 13C NMR
(CDCl3) δ 197.3, 169.8, 150.2, 143.9, 130.9, 130.5, 129.1, 127.2,
126.7, 123.6, 121.9, 121.1, 61.3, 40.6, 23.8, 22.1, 21.1. Anal.
Calcd for C17H16O4: C, 71.82; H, 5.67. Found: C, 71.67; H, 5.68.
C
12H20O3 (M+) 212.1412, found 212.1426.
6-[2-(1,3-Dioxa n -2-yl)eth yl]-2,2-bisp h en ylth iocycloh ex-
a n on e (5a ). Under a nitrogen atmosphere, to a solution of 4a
(1.72 g, 8.09 mmol) in THF (20 mL) was added LHMDS (1.0
M in THF, 9.2 mL, 9.2 mmol) at -78 °C. After being stirred
for 1 h, a solution of PhSSO2Ph (2.12 g, 8.47 mmol) in THF
(10 mL) was added. The reaction mixture was allowed to warm
to room temperature over a period of 2 h, then quenched with
aqueous NH4Cl solution and extracted with AcOEt. The extract
was dried over anhydrous Na2SO4 and concentrated in vacuo.
The residue was purified by column chromatography (hexane/
AcOEt, 5:1 to 2:1) to give monophenylthio product in 71% yield
(1.84 g) as a colorless oil. A solution of this product (1.84 g,
5.73 mmol) in THF (12 mL) was added dropwise to a slurry of
tBuOK (683 mg, 6.09 mmol) in THF (20 mL), at 0 °C, under a
nitrogen atmosphere. The reaction mixture was stirred for 30
min, and a solution of PhSSO2Ph (1.44 g, 5.76 mmol) in THF
(10 mL) was added. The reaction mixture was stirred for 2 h,
quenched with saturated aqueous NH4Cl solution, extracted
with AcOEt, dried over anhydrous Na2SO4, filtered, and
concentrated in vacuo. Purification by column chromatography
(hexane/AcOEt, 5:1) afforded 5a as a white solid in 97% yield
11-Acetoxy-1-n a p h th osu ber on e (3h ). Compound 3h was
obtained in 60% yield (65 mg) as a waxy white solid by the
reaction of homophthalic anhydride 1a (65 mg, 0.4 mmol) with
enone 2c (94 mg, 0.4 mmol) in the presence of NaH (15 mg of
60% in paraffin oil, 0.44 mmol) in 4 mL of dioxane: mp 76 °C
(CH2Cl2/hexane); IR (KBr) 1767, 1695 cm-1; 1H NMR (CDCl3)
δ 7.94-7.47 (5H, m), 2.93 (2H, dd, J ) 6.5, 6.0 Hz), 2.68 (2H,
dd, J ) 6.5, 5.0 Hz), 2,40 (3H, s), 1.91-1.67 (4H, m); 13C NMR
(CDCl3) δ 206.6, 169.6, 143.2, 135.3, 135.1, 129.8, 127.8, 127.2,
126.3, 125.8, 124.7, 122.3, 41.3, 32.5, 26.3, 21.4, 20.9. Anal.
Calcd for C15H16O3: C, 76.10; H, 6.01. Found: C, 75.85; H, 6.01.
11-Acetoxy-6-p h en ylth io-1-n a p h th osu ber on e (3i). Com-
pound 3i was obtained as a white solid in 52% yield (59 mg)
by the reaction of homophthalic anhydride 1b (81 mg, 0.3
mmol) with enone 2c (70.2 mg, 0.3 mmol) in the presence of
NaH (11.2 mg of 60% in paraffin oil, 0.33 mmol) in 4 mL of
dioxane: mp 132 °C (CH2Cl2/hexane); IR (KBr) 1775, 1700
cm-1; 1H NMR (CDCl3) δ 8.56 (1H, d J ) 7.5 Hz), 8.02 (1H, d,
J ) 7.5), 7.60-7.51 (2H, m), 7.17-6.92 (5H, m), 3.31 (2H, bs),
2.66 (2H, bs), 2.43 (3H, s), 1.73 (4H, bs); 13C NMR (CDCl3) δ
206.4, 169.4, 144.4, 142.0, 138.1, 137.3, 130.4, 129.1, 128.9,
127.1, 126.9, 126.7, 125.9, 125.1, 124.6, 122.8, 40.6, 30.2, 25.2,
21.0, 20.4. Anal. Calcd for C23H20O3S: C, 73.38; H, 5.35; S, 8.52.
Found: C, 73.32; H, 5.44; S, 8.48.
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(2.39 g): mp 84-87 °C; IR (KBr) 1705, 1582 cm-1; H NMR
(CDCl3) (500 MHz) δ 7.65-7.60 (4H, m), 7.39-7.31 (6H, m),
4.42 (1H, dd, J ) 5.5, 5.0 Hz), 4.09-4.05 (2H, m), 3.75-3.68
(2H, m), 3.26 (1H, ddt, J ) 12.0, 6.0, 6.0 Hz), 2.22-2.00 (5H,
m), 1.80-1.65 (2H, m), 1.47-1.23 (5H, m); HRMS calcd for
C
24H28O3S2 (M+) 428.1480, found 428.1474.
1-Acet oxy-2-a cet yl-3-p h en yln a p h t h a len e (3j). Com-
pound 3j was obtained as a colorless oil in 49% yield (90 mg)
by the reaction of homophthalic anhydride 1a (97.2 mg, 0.6
mmol) with acyclic enone 2d (163 mg, 0.6 mmol) in the
presence of NaH (23 mg of 60% in paraffin oil, 0.66 mmol) in
6 mL of dioxane: IR (KBr) 1770, 1700 cm-1; 1H NMR (CDCl3)
δ 7.91-7.87 (2H, m), 7.79 (1H, s), 7.59-7.42 (7H, m), 2.44 (3H,
s), 1.97 (3H, s); 13C NMR (CDCl3) δ 203.1, 169.5, 142.9, 139.7,
136.6, 134.2, 131.4, 128.9, 128.8, 128.1, 128.0, 127.9, 127.2,
126.9, 125.9, 122.1, 31.4, 20.7; HRMS calcd for C20H16O3 (M+)
304.1099, found 304.1102.
1-Ace t oxy-2-a ce t yl-3-p h e n yl-4-p h e n ylt h ion a p h t h a -
len e (3k ). Compound 3k was obtained by the reaction of
homophthalic anhydride 1b (108 mg, 0.4 mmol) with enone
2d (108 mg, 0.4 mmol) in the presence of NaH (15 mg of 60%
in paraffin oil, 0.44 mmol) in 5 mL of dioxane, as an oil in
48% yield (79 mg): IR (KBr) 1770, 1720 cm-1; 1H NMR (CDCl3)
δ 8.57 (1H, m), 7.94 (1H, m), 7.60 (2H, m), 7.35-7.21 (5H, m),
7.10-7.01 (3H, m), 6.84-6.81 (2H, m), 2.44 (3H, s), 1.86 (3H,
s); 13C NMR: δ 202.3, 169.1, 143.7, 142.9, 138.4, 138.2, 136.0,
133.3, 130.1, 129.0, 128.8, 128.1, 127.9, 127.64, 127.61, 127.2,
127.1, 126.7, 125.1, 122.5, 31.1, 20.8; HRMS calcd for C26H20O3S
(M+) 412.1133, found 412.1134.
6-[2-(1,3-Dioxa n -2-yl)eth yl]-2-p h en ylth io-2-cycloh exen -
1-on e (6a ). To a solution of 5a (2.39 g, 5.57 mmol) in CH2Cl2
(50 mL) was added m-CPBA (80% purity, 1.2 g, 5.57 mmol) at
-65 °C. After being stirred for 2.5 h, the reaction mixture was
quenched with saturated aqueous Na2S2O3 solution and ex-
tracted with CH2Cl2. The extract was washed with saturated
aqueous NaHCO3 solution, dried over anhydrous Na2SO4, and
concentrated in vacuo. The residue was purified by column
chromatography (hexane/AcOEt, 3:1) to give 6a (1.6 g, 88%)
1
as a colorless oil: IR (KBr) 1680, 1674, 1582 cm-1; H NMR
(CDCl3) (500 MHz) δ 7.42-7.29 (5H, m), 6.41 (1H, dd, J ) 5.0,
4.0 Hz), 4.54 (1H, dd, J ) 6.0, 5.0 Hz), 4.10-4.06 (2H, m),
3.78-3.72 (2H, m), 2.45-2.31 (3H, m), 2.12-1.94 (3H, m),
1.81-1.49 (4H, m), 1.33 (1H, br d, J ) 13.5 Hz); HRMS calcd
for C18H22O3S (M+) 318.1290, found 318.1293.
6-[2-(1,3-Dioxa n -2-yl)et h yl]-2-p h en ylsu lfin yl-2-cyclo-
h exen -1-on e (2e). To a solution of 6a (1.5 g, 4.71 mmol) in
CH2Cl2 (50 mL) was added m-CPBA (80% purity, 1.02 g, 4.71
mmol), at -50 °C. After being stirred at the same temperature
for 1 h, the reaction mixture was quenched with saturated
aqueous Na2S2O3 solution and extracted with CH2Cl2. The
extract was washed with saturated aqueous NaHCO3 solution,
dried over anhydrous Na2SO4, and concentrated in vacuo. The
residue was purified by column chromatography (hexane/
AcOEt, 1:1 to 1:3) to give 2e as colorless crystals: mp 76-77
°C (AcOEt/hexane); IR (KBr) 1675, 1610, 1580 cm-1; 1H NMR
(CDCl3) δ 7.73-7.64 (3H, m), 7.44-7.42 (3H, m), 4.49 (1/2H,
t, J ) 4.5 Hz), 4.39 (1/2H, t, J ) 4.5 Hz), 4.07-4.00 (2H, m),
3.76-3.63 (2H, m), 2.77-1.28 (11H, m). Anal. Calcd for
1-Acetoxy-2-acetyl-4-m eth oxy-3-ph en yln aph th alen e (3l).
Compound 3l was obtained by the reaction of homophthalic
anhydride 1c (57.6 mg, 0.3 mmol) with enone 2d (81 mg, 0.3
mmol) in the presence of NaH (11.2 mg of 60% in paraffin oil,
0.33 mmol) in 4 mL of dioxane, as an oil in 41% yield (36 mg):
IR (KBr) 1765, 1700 cm-1; 1H NMR δ: 8.21 (1H, m), 7.86 (1H,
m), 7.64-7.39 (7H, m), 3.49 (3H, s), 2.41 (3H, s), 1.87 (3H, s);
13C NMR δ: 202.6, 169.6, 151.4, 138.5, 135.3, 132.8, 130.3,
C
18H22O4S: C, 64.65; H, 6.63; S, 9.59. Found: C, 64.43; H, 6.46;
S, 9.44.