Diisopropylamine → HCID 54358533, compound

HRID 1587626Notes

Reaction equation

HRID 1587626 reaction equation
[CH3:1][CH:2]([C@@H:13]1[C@:30]2([CH3:31])[C@H:16]([C:17]3[C@H:27]([CH2:28][CH2:29]2)[C@:25]2([CH3:26])[C:20]([CH2:21][C@@H:22]([O:36][C:37](=[O:39])[CH3:38])[CH2:23][C@@H:24]2[O:32][C:33](=[O:35])[CH3:34])=[CH:19][CH:18]=3)[CH2:15][CH2:14]1)[CH2:3][S:4]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)(=[O:6])=[O:5].C([N-]C(C)C)(C)C.[Li+].C([Li])CCC.C(NC(C)C)(C)C.[O:60]1[CH:62]([CH:63]([CH3:65])[CH3:64])[CH2:61]1.[Cl-].[NH4+]>O1CCCC1.C(OCC)C.CCCCCC>[C:33]([O:32][C@@H:24]1[C@@:25]2([CH3:26])[C:20](=[CH:19][CH:18]=[C:17]3[C@@H:27]2[CH2:28][CH2:29][C@@:30]2([CH3:31])[C@H:16]3[CH2:15][CH2:14][C@@H:13]2[C@H:2]([CH3:1])[CH:3]([S:4]([C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)(=[O:6])=[O:5])[CH2:61][CH:62]([OH:60])[CH:63]([CH3:65])[CH3:64])[CH2:21][C@@H:22]([O:36][C:37](=[O:39])[CH3:38])[CH2:23]1)(=[O:35])[CH3:34]

Participants

10

Reactant 6

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 1026181,2-Epoxy-3-methylbutaneHCID 2724682Lithium diisopropylamideHCID 67789050HCID 67789050, compoundHCID 178418339Butyllithium

Product 1

HCID 54358533HCID 54358533, compoundYield 40.4%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-30 °C

Procedure

In 2 ml of tetrahydrofuran was dissolved 45 mg of 20-methyl-1α,3β-diacetoxy-21-phenylsulfonylpregna-5,7-diene and the solution was cooled in a dry ice-acetone bath under argon atmosphere. A 0.35-ml portion of a lithium diisopropylamide solution prepared from 2 ml of a 1.5N hexane solution of butyllithium and 0.5 ml of diisopropylamine in 10 ml of tetrahydrofuran was added and the resulting mixture was stirred at -30° C. for 30 minutes. The mixture was again cooled in a dry ice-acetone bath and then a solution of 150 mg of 1,2-epoxy-3-methylbutane in 1 ml of tetrahydrofuran was added, and the resulting mixture was stirred at -30° C. to -20° C. for 6 hours. A saturated aqueous solution of ammonium chloride was added to the reaction mixture and the mixture was allowed to warm to ambient temperature. Diethyl ether was then added to the reaction mixture, the organic layer was separated, and the aqueous layer was extracted with diethyl ether. The organic layer was combined, washed in sequence with an aqueous solution of sodium hydrogen carbonate and an aqueous solution of sodium chloride, then dried over sodium sulfate and concentrated. The residue was purified by silica gel thin layer chromatography to give 21 mg of 1α,3β-diacetoxy-22-phenylsulfonylcholesta-5,7-dien-24-ol.

Workup

  1. temperaturethe solution was cooled in a dry ice-acetone bath under argon atmosphere
  2. additionwas added
  3. temperatureThe mixture was again cooled in a dry ice-acetone bath
  4. stirringthe resulting mixture was stirred at -30° C. to -20° C. for 6 hours
  5. temperatureto warm to ambient temperature
  6. customthe organic layer was separated
  7. extractionthe aqueous layer was extracted with diethyl ether
  8. washwashed in sequence with an aqueous solution of sodium hydrogen carbonate
  9. dry with materialan aqueous solution of sodium chloride, then dried over sodium sulfate
  10. concentrationconcentrated
  11. customThe residue was purified by silica gel thin layer chromatography

Sources & evidence

ORD record
ord-1e94cfd3fe8f4277a7fa864006f8d082
Source dataset
uspto-grants-1993_06
Patent number
US05218109

Reaction notes

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