Nitrogen → HCID 54170027, compound

HRID 234728Notes

Reaction equation

HRID 234728 reaction equation
[O:1]=[C:2]1[CH:26]=[C:25]2[C@:20]([CH3:38])([CH2:21][CH2:22][C@H:23]([O:27][Si:28]([CH:35]([CH3:37])[CH3:36])([CH:32]([CH3:34])[CH3:33])[CH:29]([CH3:31])[CH3:30])[CH2:24]2)[C@@H:19]2[C@@H:3]1[C@H:4]1[C@:16]([CH3:39])([CH2:17][CH2:18]2)[C@@H:7]([C@H:8]([CH3:15])[CH2:9][CH2:10][C:11]([O:13]C)=[O:12])[CH2:6][CH2:5]1.O[Li].O.N#N>CC(O)(C)C.O>[O:1]=[C:2]1[CH:26]=[C:25]2[C@:20]([CH3:38])([CH2:21][CH2:22][C@H:23]([O:27][Si:28]([CH:29]([CH3:31])[CH3:30])([CH:35]([CH3:37])[CH3:36])[CH:32]([CH3:33])[CH3:34])[CH2:24]2)[C@@H:19]2[C@@H:3]1[C@H:4]1[C@:16]([CH3:39])([CH2:17][CH2:18]2)[C@@H:7]([C@H:8]([CH3:15])[CH2:9][CH2:10][C:11]([OH:13])=[O:12])[CH2:6][CH2:5]1

Participants

6

Reactant 3

HCID 947NitrogenHCID 168937Lithium hydroxide, monohydrateHCID 57250906HCID 57250906, compound

Product 1

HCID 54170027HCID 54170027, compoundYield 94%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6386tert-ButanolSolvent

Procedure

Methyl 7-oxo-3β-triisopropylsilyloxychol-5-en-24-oate (3) (5.85 g, 10.5 mmoles) was dissolved with warming in t-BuOH (100 ml). A solution of LiOH.H2O (1.76 g, 41.9 mmoles) in H2O (33 ml) was added, and the two phase mixture was heated at 80° with magnetic stirring in an N2 atmosphere for 2 hrs. Most of the t-BuOH was evaporated in vacuo, the residue-diluted with H2O (~50 ml), and acidified with 2N HCl (22 ml). The gummy suspension was extracted with CH2Cl2 (4 times). The extracts were washed with H2O and saturated brine and dried (MgSO4). Evaporation in vacuo gave 5.38 g of 4 as a gummy solid. NMR (CDCl3): δ0.68 (s, 3H, 18-Me); 0.95 (d, 3H, 20-Me); 1.05 (s, 18H, TIPS Me); 1.20 (s, 3H, 19-Me); 3.68 (m, 1H, 3-H); 5.67 (s, 1H, 6-H).

Workup

  1. temperaturethe two phase mixture was heated at 80°
  2. customMost of the t-BuOH was evaporated in vacuo
  3. additionthe residue-diluted with H2O (~50 ml)
  4. extractionThe gummy suspension was extracted with CH2Cl2 (4 times)
  5. washThe extracts were washed with H2O and saturated brine
  6. dry with materialdried (MgSO4)
  7. customEvaporation in vacuo

Sources & evidence

ORD record
ord-7ac13611a3134467abdf685611a44de5
Source dataset
uspto-grants-1997_01
Patent number
US05595996

Reaction notes

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