Arkivoc 2019, vi, 0-0
Borowiecki, P. et al.
temperature was then increased to 100 °C, using a 200 W MW-source with a holding time of 2.5 or 5 min,
respectively (depending on the experiment performed, maximum pressure inside the MW reactor was in the
range of 2-4 bars). Afterwards, the reaction was stopped by bringing the content of the vial to room
temperature by cooling the jet for 1 min. Next, the crude reaction mixture was dissolved in acetone (3 mL),
the immobilized catalyst was removed by filtration under suction, then rinsed with additional portion of
acetone (3 mL), and the resulting permeate was evaporated to dryness using rotapovator. The crude oil
residues were purified by silica gel column chromatography using gradient of mixture of CHCl3/acetone (99:1,
98:2, 95:5, v/v) to afford the 17β-testosterone esters 2a–e in 23–96% yield, respectively. Physical and spectral
data of 2a–e were consistent with the one reported in literature and those obtained via classical route using
(Et3N/DMAP)-catalytic system. Attention: The removed p-TsOH catalyst after washing with acetone was dried
on standing and used directly in the next charge without additional treatment.
Testosterone acetate (2a). mp 135.5–136 °C (CHCl3/acetone) [Lit.:81 136–137 °C (no data)]; 1H NMR (500 MHz,
CDCl3): δ 0.81 (s, 3H), 0.82–1.11 (s, 3H), 1.16 (s, 3H), 1.26–1.92 (m, 10H), 2.01 (s, 3H), 2.09–2.48 (m, 6H), 4.57
(dd, J=9.3, 7.8 Hz, 1H), 5.69 (s, 1H); 13C NMR (126 MHz, CDCl3): δ 12.0, 17.4, 20.5, 21.1, 23.4, 27.5, 31.5, 32.7,
33.9, 35.4, 35.7, 36.6, 38.6, 42.4, 50.2, 53.7, 82.4, 123.9, 170.9, 171.1, 199.4 [The NMR spectral data were
accordance with those reported in the literature42]; IR (nujol): νmax = 1736, 1664, 1618, 1445, 1329, 1267,
+
1248, 1182, 1116, 1044, 1025, 935, 862, 725; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C21H31O3 m/z: 331.2273,
Found 331.2151; [α]D29 = +101.00 (c 0.50, CHCl3) {Lit.82 [α]D = +93.10 (c 1.00, CHCl3) or lit.:62 [α]D25 = +82.30 (c
1.00, CHCl3)}; HPLC [n-hexane-2-PrOH (85:15, v/v); f = 0.8 mL/min; λ = 254 nm]: tR= 12.792 or [n-hexane-2-
PrOH (90:10, v/v); f = 0.8 mL/min; λ = 254 nm]: tR = 16.736 or [n-hexane-2-PrOH (95:5, v/v); f = 0.8 mL/min; λ =
254 nm]: tR = 26.785; UV/VIS: λmax = 242 nm (EtOH).
1
Testosterone propionate (2b). mp 121–122 °C (CHCl3/acetone) [Lit.:83 121–123 °C (no data)]; H NMR (500
MHz, CDCl3): δ 0.83 (s, 3H), 0.90–1.24 (m, 9H), 1.28–1.90 (m, 10H), 1.97–2.05 (m, 1H), 2.11–2.46 (m, 7H), 4.60
(dd, J=9.2, 8.0 Hz, 1H), 5.72 (d, J=0.7 Hz, 1H); 13C NMR (126 MHz, CDCl3): δ 9.24, 12.0, 17.4, 20.5, 23.5, 27.5,
27.8, 31.5, 32.7, 33.9, 35.4, 35.7, 36.6, 38.6, 42.5, 50.3, 53.7, 82.2, 123.9, 170.9, 174.5, 199.4 [The NMR
spectral data were accordance with those reported in the literature84]; IR (nujol): νmax = 1740, 1725, 1681,
+
1668, 1452, 1270, 1229, 1188, 1076, 1041, 1019, 870, 714; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C22H33O3
m/z: 345.2425, Found 345.2173; [α]D26 = +98.00 (c 0.50, CHCl3) {Lit.:46 [α]D25 = +63.00 (c 2.30, CHCl3)}; HPLC [n-
hexane-2-PrOH (85:15, v/v); f = 0.8 mL/min; λ = 254 nm]: tR = 11.618; UV/VIS: λmax = 244 nm (EtOH).
Testosterone butanoate (2c). mp 107–110 °C (CHCl3/acetone) [Lit.:85 108.85 °C (no data)]; H NMR (500 MHz,
1
CDCl3): δ 0.81 (s, 3H), 0.92 (t, J=3.4 Hz, 3H), 0.95–1.10 (m, 1H), 1.16 (s, 3H), 1.26–1.90 (m, 13H), 1.95–2.05 (m,
1H), 2.09–2.45 (m, 8H), 4.59 (t, J=8.6 Hz, 1H), 5.70 (s, 1H); 13C NMR (126 MHz, CDCl3): δ 12.0, 13.6, 17.4, 18.5,
20.5, 23.5, 27.5, 31.5, 32.7, 33.9, 35.4, 35.7, 36.4, 36.6, 38.6, 42.5, 50.2, 53.7, 82.1, 123.9, 170.8, 173.6, 199.3
[The NMR spectral data were accordance with those reported in the literature46]; IR (nujol): νmax = 1724, 1668,
1615, 1414, 1351, 1267, 1229, 1188, 1132, 1101, 1047, 1013, 941, 864; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
+
29
25
C23H35O3 m/z: 359.2586, Found 359.2327; [α]D = +103.00 (c 0.50, CHCl3) {Lit.:46 [α]D = +78.00 (c 1.71,
CHCl3)}; HPLC [n-hexane-2-PrOH (85:15, v/v); f = 0.8 mL/min; λ = 254 nm]: tR = 10.752; UV/VIS: λmax = 246 nm
(EtOH).
Testosterone decanoate (2d). mp 53–54.5 °C (CHCl3/acetone) [Lit.:83 55–57 °C (no data)]; H NMR (500 MHz,
1
CDCl3): δ 0.83 (s, 3H), 0.87 (t, J=6.9 Hz, 3H), 0.91–1.11 (m, 3H), 1.18 (s, 3H), 1.20–2.53 (m, 32H), 4.60 (t, J=8.8
Hz, 1H), 5.72 (s, 1H); 13C NMR (126 MHz, CDCl3): δ 12.0, 14.1, 17.4, 20.5, 22.6, 23.5, 25.1, 27.5, 29.1, 29.2, 29.2,
29.4, 31.5, 31.8, 32.7, 33.9, 34.6, 35.4, 35.7, 36.6, 38.6, 42.5, 50.3, 53.7, 82.1, 123.9, 170.9, 173.8, 199.4 [The
NMR spectral data were accordance with those reported in the literature46]; IR (nujol): νmax = 1721, 1680,
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