Reaktion #70362

ord-f0a4f3cfe50545289c007eb866310695

Reaktionsgleichung

C[C@]12CCCCC1[C@@H](O[N+](=O)[O-])C[C@@H]1[C@@H]2CC[C@@]2(C)[C@H]1CC13OCCOC12OCCO3
17,17-bis(ethylendioxy)androstane-6α-yl nitrate
O
H2O
O=C([O-])O.[Na+]
NaHCO3
Cc1ccc(S(=O)(=O)O)cc1
pTSA
→
C[C@]12CCC(=O)CC1[C@@H](O[N+](=O)[O-])C[C@@H]1[C@@H]2CC[C@]2(C)C(=O)CC[C@@H]12
title compound
C[C@]12CCC(=O)CC1[C@@H](O[N+](=O)[O-])C[C@@H]1[C@@H]2CC[C@]2(C)C(=O)CC[C@@H]12
3,17-Dioxoandrostane-6α-yl nitrate

Edukte

C[C@]12CCCCC1[C@@H](O[N+](=O)[O-])C[C@@H]1[C@@H]2CC[C@@]2(C)[C@H]1CC13OCCOC12OCCO3
17,17-bis(ethylendioxy)androstane-6α-yl nitrate
O
H2O
O=C([O-])O.[Na+]
NaHCO3
Cc1ccc(S(=O)(=O)O)cc1
pTSA

Reagenzien

Keine

Lösungsmittel

CC(C)=O
acetone
CC(C)=O
acetone

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Sonstigewas evaporated
  2. 2
    ExtraktionThe aqueous phase was extracted with CH2Cl2 (3×50 mL)
  3. 3
    WaschenThe combined organic extracts were washed with H2O
  4. 4
    Trocknendried over Na2SO4
  5. 5
    Sonstigeevaporated to dryness
  6. 6
    SonstigeThe residue was purified by flash chromatography (SiO2, cyclohexane/Acetone/CH2Cl2 70/15/15)

Vorschrift

A solution of 3,3:17,17-bis(ethylendioxy)androstane-6α-yl nitrate (2.50 g) and pTSA.H2O (6.05 g) in acetone (150 mL) was stirred at room temperature for 1.5 h. The solution was neutralized by addition of 5% aqueous NaHCO3, and acetone was evaporated. The aqueous phase was extracted with CH2Cl2 (3×50 mL). The combined organic extracts were washed with H2O, dried over Na2SO4 and evaporated to dryness. The residue was purified by flash chromatography (SiO2, cyclohexane/Acetone/CH2Cl2 70/15/15) to give the title compound II-ab as a white solid (1.66 g, 75%). 1H-NMR (300 MHz, acetone-d6, ppm from TMS): δ 5.09 (1H, ddd), 2.60-0.95 (17H, m), 1.25 (3H, s), 0.90 (3H, s).

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08536160B2uspto-grants-2013_09