Ammonia → HCID 25142820, compound

HRID 2038536Notes

Reaction equation

HRID 2038536 reaction equation
C([S:8][C:9]1(SCC2C=CC=CC=2)[CH2:14][CH2:13][C@H:12]2[C@H:15]3[C@H:25]([CH2:26][CH2:27][C@:10]12[CH3:11])[C@:23]1([CH3:24])[C@H:18]([CH2:19][C@H:20]([OH:28])[CH2:21][CH2:22]1)[CH2:17][CH2:16]3)C1C=CC=CC=1.N>C1COCC1.CCOCC>[OH:28][C@@H:20]1[CH2:21][CH2:22][C@@:23]2([CH3:24])[C@@H:18]([CH2:17][CH2:16][C@@H:15]3[C@@H:25]2[CH2:26][CH2:27][C@@:10]2([CH3:11])[C@H:12]3[CH2:13][CH2:14][C:9]2=[S:8])[CH2:19]1

Participants

4

Reactant 2

HCID 222AmmoniaHCID 86652498HCID 86652498, compound

Product 1

HCID 25142820HCID 25142820, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 21868444Ether tetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

17,17-Bisbenzylthio-5α-androstane-3α-ol (3.76 g, 7.22 mmol) in THF/Et2O (40:100 mL) was added in a dropwise manner to a suspension of Na (3.32 g, 144.4 mmol) in liquid NH3 at −78° C. under N2. The blue suspension was allowed to stir at −78° C. for 3 h. The reaction was then quenched by the addition of saturated NH4Cl (50 mL) and H2O (150 mL). The resulting biphasic mixture was extracted with CH2Cl2 (3×200 mL). The extracts were combined, dried (MgSO4), and concentrated to provide an orange semisolid. The semisolid was purified on silica using medium pressure column chromatography (petroleum ether/acetone, 8:2). The resulting solid was recrystallized from EtOAc/hexane to provide a salmon colored solid (1.06 g, 48%). mp. 172-173° C. 1H-NMR (300 MHz, CDCl3) δ 0.82 (s, 3H), 0.89 (s, 3H), 0.90-1.68 (m, 21H), 1.99-2.03 (m, 2H), 2.59-2.69 (ddd, J=9, 9, 21 Hz, 1H), 2.90-3.00 (dd, J=9, 9 Hz, 1H), 4.06 (m, 1H). Elemental Anal. for C19H30OS Calcd. C, 74.45; H, 9.87; S, 10.46. Found. C, 74.33; H, 10.01; S, 10.47.

Workup

  1. customThe reaction was then quenched by the addition of saturated NH4Cl (50 mL) and H2O (150 mL)
  2. extractionThe resulting biphasic mixture was extracted with CH2Cl2 (3×200 mL)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customto provide an orange semisolid
  6. customThe semisolid was purified on silica using medium pressure column chromatography (petroleum ether/acetone, 8:2)
  7. customThe resulting solid was recrystallized from EtOAc/hexane

Sources & evidence

ORD record
ord-4c07360d62a04635ab004f940e4fa5f3
Source dataset
uspto-grants-2013_11
Patent number
US08575375B2

Reaction notes

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