Molecules 2002, 7
788
(d, J = 5.5 Hz, 3H), 1.38 (s, 11H), 1.47 – 1.59 (m, 6H), 2.32 (s, 3H), 2.55 (t, J = 7.8 Hz, 2H), 2.73 (t, J
= 6.2 Hz, 2H), 2.88 (t, J = 6.4 Hz, 2H), 3.76 (s, 3H), 3.78 (s, 3H), 3.80 – 3.90 (m, 1H), 4.76 (s, 1H),
6.62 (s, 1H), 6.64 (s, 1H); 13C NMR (CDCl3) δ 21.48, 28.37, 28.64, 28.99, 29.11, 29.42, 29.90, 30.12,
30.58, 36.65, 47.51, 55.92, 56.03, 78.63, 112.76, 113.91, 124.69, 129.89, 151.17, 151.36, 155.37,
195.95; Calculated: C = 63.54%, H = 8.67%, N = 3.09%, S = 7.07%; found: C = 63.51%, H = 8.72%,
N = 3.16%, S = 7.11%
6-(2,5-Dimethoxy-4-(2-[N-(tert-butoxycarbonyl)]aminopropyl)phenyl)hexyl thiol (13)
6-(2,5-Dimethoxy-4-(2-[N-(tert-butoxycarbonyl)]aminopropyl)phenyl)hexyl thioacetate (12, 51 mg,
0.11 mmols) was dissolved in methanol (5 mL) and methanolic ammonia (25 mL) was added. The
mixture was stirred at 22°C for 3 hours and evaporated. This gave a yellow tar which was dissolved in
dichloromethane (50mL), the organic solution was washed with water (1 x 20mL) and dried over
magnesium sulfate. After filtering it was evaporated and purified using silica gel column
chromatography (1:1 ethyl acetate-hexanes). This gave 40 mg (88%) of compound 13 as a colorless
1
solid, m.p. = 99-100°C; Rf = 0.57 (silica, 1:1 ethyl acetate-hexanes); H-NMR: δ 1.05 (d, J = 6.5 Hz,
3H), 1.13 – 1.59 (m, 17H), 2.41 – 2.70 (m, 6H), 3.69 (s, 3H), 3.71 (s, 3H), 3.76- 3.77 (m, 1H), 4.69 (s,
1H), 6.55 (s, 1H), 6.58 (s, 1H); 13C-NMR: 20.44, 24.16, 27.94, 28.58, 28.69, 29.50, 30.15, 33.51,
38.64, 47.05, 55.49, 55.60, 78.23, 112.33, 113.48, 124.27, 129.45, 150.75, 150.93, 154.95; Calculated:
C = 64.20%, H = 9.06%, N = 3.40%, S = 7.79%; found: C = 64.04%, H = 8.95%, N = 3.41%, S =
7.68%
6-(2,5-Dimethoxy-4-(2-aminopropyl)phenyl)hexyl thiol (14)
Method A: 6-(2,5-Dimethoxy-4-(2-[N,N-phthalimido]propyl)phenyl)hexyl thioacetate (9, 230 mg, 0.47
mmols) was dissolved in absolute ethanol (50 mL). Hydrazine monohydrate (15 mL) was added to this
solution and the mixture was stirred at 22°C for 90 minutes. Dichloromethane (200 mL) was added and
the solution was washed with water (2 x 100 mL). The organic solution was dried over magnesium
sulfate, filtered, and evaporated. This gave100 mg (68%) of the product as a pale yellow oil; 1H-NMR:
δ 1.13 (d, J = 5.9 Hz, 3H), 1.23 (m, 1H), 1.40 (m, 6H), 1.57 (t, J = 6.0 Hz, 2H), 1.68 (t, J = 6.0 Hz,
2H), 2.40 (br s, 2H), 2.56 (t, J = 6.0 Hz, 2H), 2.68 (t, J = 7.3, 2H), 3.21 (m, 1H), 3.76 (s, 6.0 H), 6.65
(s, 2H); 13C-NMR: δ 23.26, 28.36, 29.97, 30.14, 39.11, 40.64, 47.30, 56.01, 56.13, 112.95, 114.06,
125.67, 129.82, 151.12, 151.49; LR-ESMS [M+1] 312.32; The base was converted to the corresponding
oxalate salt by dissolving 50 mg of the amine in dry ether (50 mL) and adding an ethereal solution
containing oxalic acid (100 mg) dissolved in ether (200 mL). The resulting product was removed by
filtration, washed with dry ether (2 x 100 mL) and air dried to give 20 mg of the oxalate as a colorless
solid, m.p. = 148-150°C; Calculated: C = 56.84%, H = 7.78%, N = 3.49%, S = 7.98% found: C =
57.03%, H = 7.63%, N = 3.36%, S = 7.78%.