HCID 86589971, compound → HCID 69629953, compound

HRID 1792232Notes

Reaction equation

HRID 1792232 reaction equation
C1(N2C(=O)N=NC2=O)C=CC=CC=1.[Si:14]([O:21][C@@H:22]1[C@@:39]2([CH3:40])[C:26](=[CH:27][CH:28]=[C:29]3[C@@H:38]2[CH2:37][CH2:36][C@@:34]2([CH3:35])[C@H:30]3[CH2:31][CH2:32][C@@H:33]2[CH2:41][O:42][CH2:43][CH2:44][C:45]([N:47]([CH3:49])[CH3:48])=[O:46])[CH2:25][C@@H:24]([O:50][Si:51]([C:54]([CH3:57])([CH3:56])[CH3:55])([CH3:53])[CH3:52])[CH2:23]1)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15]>CN1CCN(C)C1=O>[Si:14]([O:21][C@@H:22]1[C@@:39]2([CH3:40])[C:26](=[CH:27][CH:28]=[C:29]3[C@@H:38]2[CH2:37][CH2:36][C@@:34]2([CH3:35])[C@H:30]3[CH2:31][CH2:32][C@@H:33]2[CH2:41][O:42][CH2:43][CH2:44][C:45]([N:47]([CH3:48])[CH3:49])=[O:46])[CH2:25][C@@H:24]([O:50][Si:51]([C:54]([CH3:57])([CH3:56])[CH3:55])([CH3:52])[CH3:53])[CH2:23]1)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15]

Participants

3

Reactant 1

HCID 86589971HCID 86589971, compound

Product 1

HCID 69629953HCID 69629953, compound

Reagents, catalysts & solvents 1

HCID 66611,3-Dimethyl-2-imidazolidinoneSolvent

Conditions

Temperature
140 °C

Procedure

To 1α,3β-bis(tert-butyldimethylsilyloxy)-17β-(N,N-dimethylaminocarbonylethoxymethyl)androsta-5,7-diene 4-phenyl-1,2,4-triazoline-3,5-dione adduct (2.3 g), was added 1,3-dimethyl-2-imidazolidinone (30 ml), followed by heating at 140° C. for 3 hours. The reaction mixture was extracted with hexane, the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to remove the solvent. The resulting residue was purified by column chromatography (hexane:ethyl acetate=1:2) to give 1α,3β-bis(tert-butyldimethylsilyloxy)-17β-(N,N-dimethylaminocarbonylethoxymethyl)androsta-5,7-diene. To a suspension of anhydrous cerous (III) chloride (2.6 g) and tetrahydrofuran (8.3 ml), was added a 1.0M methylmagnesium bromide/tetrahydrofuran solution (8.7 ml) at 0° C., followed by stirring for 0.5 hours. The reaction mixture and the above-obtained 1α,3β-bis(tert-butyldimethylsilyloxy)-17β-(N,N-dimethylaminocarbonylethoxymethyl)androsta-5,7-diene (1.5 g) were mixed and reacted for 1 hour. The reaction mixture was added to a mixture of potassium hydrogen sulfate solution and hexane cooled at −10° C. in order to stop the reaction and then filtered. The organic layer was dried over anhydrous magnesium sulfate, evaporated under reduced pressure to remove the solvent and the resultant was reacted for 1 hour with Grignard solution, which was prepared as above. The thus obtained reaction mixture was worked up as above and purified by column chromatography (hexane:ethyl acetate=7:1) to give the titled compound (730 mg).

Workup

  1. extractionThe reaction mixture was extracted with hexane
  2. washthe organic layer was washed with saturated brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customevaporated under reduced pressure
  5. customto remove the solvent
  6. customThe resulting residue was purified by column chromatography (hexane:ethyl acetate=1:2)

Sources & evidence

ORD record
ord-e429c5e1fdd34ece90b3d55e435f2680
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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