Chlorotrimethylsilane → HCID 10394237, compound

HRID 893827Notes

Reaction equation

HRID 893827 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][Si:14](Cl)([CH3:16])[CH3:15].[CH3:18][O:19][CH2:20][CH2:21][O:22][CH2:23][N:24]([CH2:31][C@@:32]12[C@@H:49]3[C@H:40]([C@H:41]4[C@@:45]([CH2:47][CH2:48]3)([CH3:46])[C:44](=[O:50])[CH2:43][CH2:42]4)[CH2:39][CH2:38][C:37]1=[CH:36][C:35](=[O:51])[CH2:34][CH2:33]2)[C:25](=[O:30])[C:26]([F:29])([F:28])[F:27]>O1CCCC1.CCCCCC.C(N(CC)CC)C>[CH3:18][O:19][CH2:20][CH2:21][O:22][CH2:23][N:24]([CH2:31][C@@:32]12[C@@H:49]3[C@H:40]([C@H:41]4[C@@:45]([CH2:47][CH2:48]3)([CH3:46])[C:44]([O:50][Si:14]([CH3:16])([CH3:15])[CH3:13])=[CH:43][CH2:42]4)[CH2:39][CH2:38][C:37]1=[CH:36][C:35]([O:51][Si:14]([CH3:16])([CH3:15])[CH3:13])=[CH:34][CH2:33]2)[C:25](=[O:30])[C:26]([F:27])([F:28])[F:29]

Participants

8

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 7912DiisopropylamineHCID 10390653HCID 10390653, compoundHCID 178418339Butyllithium

Product 1

HCID 10394237HCID 10394237, compound

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
-20 °C

Procedure

To a stirred solution of diisopropylamine (1.03 ml, 7.34 mmole) in tetrahydrofuran (65 ml) under argon and cooled to -20° C. was added n-butyl lithium (2.76 ml of a 2.42M solution in hexane, 6.67 mmole). After 9 minutes, a cooled (-20° C.) solution of trimethysilyl chloride (2.82 ml, 22.24 mmole) in tetrahydrofuran (10 ml) was added slowly. After 2 minutes more, a cooled (-20° C.) solution of 19-[N-[(2-methoxyethoxy)methyl]trifluoroacetamido]androst-4-ene-3,17-dione (1.08 g, 2.22 mmole) in tetrahydrofuran (10 ml) was added dropwise. The reaction was stirred at -20° C. for 30 minutes and then allowed to warm slowly to room temperature. After 30 minutes at room temperature, triethylamine (10 ml) was added then ethyl ether (350 ml) and the organics washed with saturated sodium bicarbonate (2×100 ml), 150 ml of water-saturated aqueous sodium bicarbonate (2:1) and finally 100 ml of brine-saturated aqueous sodium bicarbonate (3:1). Drying (Na2SO4) and concentration gave 19-[N-[(2-methoxyethoxy)-methyl]trifluoroacetamido]-3,17-bis(trimethylsilyloxy)androsta-2,4,16-triene (quantitative) as a pale-yellow, viscous oil.

Workup

  1. additionwas added slowly
  2. waitAfter 2 minutes more
  3. additionwas added dropwise
  4. temperatureto warm slowly to room temperature
  5. waitAfter 30 minutes at room temperature
  6. washethyl ether (350 ml) and the organics washed with saturated sodium bicarbonate (2×100 ml), 150 ml of water-saturated aqueous sodium bicarbonate (2:1) and finally 100 ml of brine-saturated aqueous sodium bicarbonate (3:1)
  7. customDrying
  8. concentration(Na2SO4) and concentration

Sources & evidence

ORD record
ord-a7672106790b423ba878a5240a59ef2e
Source dataset
uspto-grants-1992_06
Patent number
US05126488

Reaction notes

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