The Journal of Organic Chemistry
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water (4 × 50 mL) and the aqueous portion re-extracted (2 × 25 mL).
The combined organic phases were dried over Na2SO4 and the solvent
evaporated under reduced pressure to yield a crude product which was
purified by crystallizing from cyclohexane to give a colorless solid (4.2 g,
39%): mp 85−87 °C; 1H NMR (CDCl3) δ 2.0−2.3 (m, 2H), 2.76 (d,
J = 3.2 Hz, 1H), 2.9 (m, 1H), 3.1 (m, 1H), 3.65 (td, J = 11.2, 3.09 Hz,
1H), 4.6 (s, 1H), 7.1−7.5 (m, 9H); 13C NMR (CDCl3) δ 23.8, 28.6,
52.0, 67.8, 126.2, 127.4, 128.2, 128.8, 29.2, 130.0, 132.03, 133.8, 135.7,
136.4; m/z (GC−MS) 256.1 (Found: C, 74.87; H, 6.24; S, 12.46;
C16H16OS requires C, 74.96; H, 6.29; S, 12.51); HRMS = 257.1000
(calculated for [M + H+]+, C16H16OS), 257.0994 (observed).
cis-1-Acetoxy-2-phenylthio-1,2,3,4-tetrahydronaphthalene
(11, X = PhS). To cis-1-hydroxy-2-phenylthio-1,2,3,4-tetrahydronaph-
thalene (10, X = PhS, 3.5 g, 13.6 mmol) in dry pyridine (15 mL) was
added acetic anhydride (2.1 mL, 20.4 mmol). The mixture was stirred
for 20 h at room temperature, after which water (50 mL) was added
and the pH adjusted to 5−6 using 10% hydrochloric acid (v/v) at 5−
10 °C. The aqueous phase was extracted with CHCl3 (3 × 75 mL) and
the extracts washed with water (2 × 50 mL) and saturated NaCl
solution (20 mL). The solvent was evaporated under reduced pressure to
yield an oil (3.8 g, 93%): 1H NMR (CDCl3) δ 2.07 (s, 3H), 2.09−2.35
(m, 2H), 2.88 (q, 1H), 3.06 (q, 1H), 3.60 (td, J = 11.33, 3.50 Hz, 1H)
6.20 (d, J = 3.07 Hz, 1H), 7.05−7.54 (m, 9H); 13C NMR (CDCl3) δ
21.0, 25.0, 26.6, 49.0, 70.3, 126.3, 127.2, 128.6, 128.9, 129.0, 130.0,
132.2, 134.1, 134.6, 136.1, 170.5; m/z (ES) 299.1 (M + H)+ (Found:
C, 72.1; H, 5.9; S, 10.1; C18H18O2S requires C, 72.45; H, 6.08; S,
10.7); HRMS = 321.0925 (calculated for [M + Na+]+, C18H18O2S),
321.0911 (observed).
1H), 7.21−7.27 (m, 3H), 7.42 (t, J = 7.32, Hz, 1H), 7.52 (d, J = 7.58
Hz, 1H), 7.59 (d, J = 7.53 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ
64.9, 68.7, 118.5, 124.9, 126.6, 127.9, 128.0, 129.1, 129.5, 131.2, 133.6,
134.0, 135.6, 136.4; m/z (ES) 309.1 (M + Na)+; HRMS = 309.0561
(calculated for [M + Na+]+, C16H14 O3S), 309.0563 (observed).
cis-1-Hydroxy-2-azido-1,2,3,4-tetrahydronaphthalene (10,
X = N3). To a stirred solution of ( )- trans-1-hydroxy-2-bromo-
1,2,3,4-tetrahydronaphthalene (10.5 g, 46.2 mmol) in DMF (30 mL)
was added sodium azide (3.3 g, 50.7 mmol). Stirring was continued for
20 h at 75 °C and the mixture then cooled to 25 °C and diluted with
water (150 mL). The products were extracted with chloroform (3 ×
150 mL) and the combined organic layers washed with water (5 × 100
mL) and dried over sodium sulfate. The solvent was removed to yield
a crude product, which was crystallized in cyclohexane to give an off-
1
white solid (4.5 g, 51% yield): mp 82−85 °C; H NMR (CDCl3) δ
1.95−2.44 (m, 2H and OH), 2.84 (m, 1H), 3.04 (td, J = 17.25, 5.78
Hz, 1H), 3.90 (td, J = 9.67, 3.11 Hz, 1H), 4.78 (d, J = 2.77 Hz, 1H),
7.07−7.19 (m, 1H), 7.18−7.35 (m, 2H), 7.55−7.36 (m, 1H); 13C
NMR (CDCl3) δ 22.7, 26.7, 61.7, 69.3, 126.5, 128.3, 128.6, 129.3,
135.3, 135.8; m/z (ES) 190.1(M + H)+; IR υ (cm−1) 1454, 3434
(Found: C, 63.4; H, 5.79; N, 22.17; C10H11N3O requires C, 63.48; H,
5.86; N, 22.21).
cis-1-Acetoxy-2-azido-1,2,3,4-tetrahydronaphthalene (11,
X = N3). To a stirred solution of ( ) cis-1-hydroxy-2-azido-1,2,3,4-
tetrahydronaphthalene (11, X= N3, 3.0 g, 15.8 mmol) in pyridine (15 mL)
was added acetic anhydride (6.0 mL, 58.8 mmol) at room temperature.
The mixture was stirred at 25 °C for a further 20 h, cooled to 5 °C and
the pH adjusted to 5−6 with 10% hydrochloric acid. After extraction
with chloroform (3 × 50 mL) the combined organic layers were
washed with water (3 × 50 mL) and dried over sodium sulfate. The
solvent was removed to yield an off white solid (3.0 g 82%): 1H NMR
(CDCl3) δ 2.2 (s, 3H), 2.8−2.95 (m, 2H), 3.08 (td, J = 7.27, 5.43 Hz,
2H), 3.83 (td, J = 10.14, 3.10 Hz, 1H), 6.18 (d, J = 3.13 Hz, 1H), 7.1−
7.36 (m, 4H); 13C NMR (101 MHz, CDCl3) δ 170.5, 135.9, 132.8,
129.6, 128.7, 128.7, 126.5, 70.6, 58.8, 26.8, 23.3, 21.1; m/z (EI)
232.1(M + H)+; IR υ (cm−1) 1454, 3434 (Found: C, 62.2; H, 5.61; N,
17.93; C12H13N3O2 requires C, 62.3; H, 5.67; N, 18.1).
cis-1-Hydroxy-2-phenylthio-1,2-dihydronaphthalene (6, X =
cis-PhS). cis-1-Acetoxy-2-phenylthio-1,2,3,4-tetrahydronaphthalene
(12, X = PhS, 1.0 g, 3.35 mmol) was dissolved in CCl4 (30 mL) and
N-bromosuccinimide (0.59 g, 3.35 mmol) and a catalytic quantity of
AIBN added. The mixture was heated under reflux with stirring (ca. 70 °C).
1
When reaction was complete (1.5 h, by H NMR), the mixture was
cooled to room temperature and filtered to remove succinimide.
Removal of the solvent under reduced pressure gave an oil which was
dissolved in THF (15 mL) and cooled to 0−5 °C. A 1.0 M solution of
DIBAL-H (11.1 mL, 11.2 mmol, 1.0 M solution in THF) was added
slowly over 45 min. The resultant reaction mixture was stirred for
30 min at 0−5 °C and quenched with 1.0 M HCl at −10 °C (the final
pH of the mixture is 5−6) followed by extraction with ethyl acetate (3 ×
25 mL). The combined organic phases were dried over Na2SO4 and the
solvent removed under reduced pressure to give an oil, which was
dissolved in DMSO (75 mL). Tetrabutylammonium fluoride hydrate
(1.75 g, 6.7 mmol) was added and the suspension stirred for 4 h at
25 °C, followed by dilution with water (150 mL) and extraction into
EtOAc (3 × 100 mL). The EtOAc was washed with water (6 × 100 mL),
dried and the solvent evaporated under reduced pressure to yield a
crude product which was purified by preparative TLC (30% ethyl
cis-1-Hydroxy-2-azido-1,2-dihydronaphthalene (6, X = cis-
N3). cis-1-Acetoxy-2-azido-1,2,3,4-tetrahydronaphthalene (11, X = N3,
0.5 g, 2.16 mmol) was dissolved in dry CCl4 (20 mL) and N-
bromosuccinimide (0.38 g, 2.16 mmol) and a catalytic quantity of
AIBN added. The mixture was heated under reflux (ca. 70 °C) and on
1
completion of the reaction (1.5 h, by H NMR), cooled to room
temperature and filtered to remove succinimide. Removal of the
solvent under reduced pressure gave the crude bromo compound as an
oil, which was dissolved in dry THF (25 mL) cooled to 0 °C and
sodium methoxide (0.23 g, 4.32 mmol) added. The mixture was stirred
for 3 h at 0 °C and left overnight in a freezer. Cold diethyl ether (15 mL)
was added and salts removed by filtration through Celite. The filtrate
was quickly washed with cold water (20 mL) and dried over Na2SO4
followed by evaporation under reduced pressure. The crude product
was purified by preparative TLC (20% ethyl acetate in pentane) to
yield an off-white solid (0.1 g, 33%): mp 75−77 °C; 1H NMR
(CDCl3) δ 2.27 (d, J = 9.83 Hz, 1H), 4.15 (t, J = 5.13 Hz, 1H), 4.89
(dd, J = 9.71, 5.11 Hz, 1H), 6.07 (dd, J = 9.57, 5.17 Hz, 1H), 6.78 (d,
J = 9.57 Hz, 1H), 7.15 (m, 1H), 7.3 (m, 2H), 7.57 (d, J = 7.23 Hz, 1H);
13C NMR (CDCl3) 59.6, 70.2, 122.0, 125.8, 127.0, 128.4, 129.0, 131.4,
1
acetate in pentane) to give a cream-colored solid (0.2 g, 24%): H
NMR (CDCl3) δ 2.9 (d, J = 10.3 Hz, OH), 4.09 (t, J = 5.85 Hz, 1H),
5.06 (dd, J = 10.2, 6.1 Hz, 1H), 6.12 (dd, J = 9.5, 5.6 Hz, 1H), 6.46 (d,
J = 9.5 Hz, 1H), 6.9 (d, J = 7.4 Hz, 1H), 7.1−7.3 (m, 7H), 7.55 (d, J =
7.5 Hz, 1H); 13C NMR (CDCl3) δ 52.2, 69.1, 125.1, 125.9, 126.2,
127.5, 127.8, 128.3, 128.5, 129.1, 132.1, 132.9, 133.3, 136.5; m/z (ES)
255 (M + H)+; HRMS = 255.0844 (calculated for [M + H+]+,
C16H14OS), 255.0838 (observed).
cis-1-Hydroxy-2-phenylsulfonyl-1,2-dihydronaphthalene (6, X =
cis-PhSO2). To an ice-cold solution of cis-1-hydroxy-2-phenylthio-1,2-
dihydronaphthalene (6, X = cis-PhS, 40 mg, 0.157 mmol) in CHCl3
(10 mL) was added m-chloroperbenzoic acid (54 mg, 0.31 mmol) over
15 min with stirring. The reaction mixture was allowed to come to
room temperature and stirred for 2 h. When the starting material had
been consumed (TLC), undissolved benzoic acid was removed by
filtration and the solvent evaporated under reduced pressure. The
crude product was purified by column chromatography (ethyl acetate/
pentane mixtures) to yield the product as a light brown liquid (25 mg,
132.1, 135.8; HRMS = 188.0824 (calculated for [M + H+]+, C10H9N3O),
188.0832 (observed).
cis-1-Hydroxy-2-amino-1,2-dihydronaphthalene (6, X = cis-
NH2). To a solution of cis-1-hydroxy-2-azido-1,2-dihydronaphthalene9
(6, X = cis-N3, 0.05 g, 0.26 mmol) in anhydrous THF (5 mL) was
added a mixture of zinc powder (0.17 g, 2.67 mmol) and cobalt
chloride hexahydrate (0.76 g, 3.2 mmol) under a nitrogen atmosphere.
After 45 min TLC showed that starting material had been consumed
and the reaction mixture was diluted with 15 mL of THF and filtered.
Evaporation of the filtrate gave a crude product which was purified by
flash column chromatography (EtOAc/hexane, MeOH) to yield a light
1
56%): H NMR (CDCl3) δ 4.15 (t, J = 5.64 Hz, 1H), 5.21 (m, J =
1
5.97 Hz, 1H), 6.07 (dd, J = 9.56, 5.51 Hz, 1H), 6.53 (d,
J = 9.54, Hz, 1H), 6.65 (d, J = 7.36, Hz, 1H), 7.05 (t, J = 7.64 Hz,
brown oil (0.035 g, 81%): H NMR (CD3OD) δ 3.49 (t, 1H), 3.54−
3.58 (m, 3H, OH and NH2), 4.58 (d, J = 5.04 Hz, 1H), 5.91 (dd, J = 9.64,
570
dx.doi.org/10.1021/jo2020483 | J. Org. Chem. 2012, 77, 563−572