1,3-Propanediol → HCID 15858861, compound

HRID 1418731Notes

Reaction equation

HRID 1418731 reaction equation
[O:1]1[C@H]2[C@H](O)C[C:6]3[C@:27]([CH3:28])([C@@H:2]12)[C@@H:26]1[C:9]([C@H:10]2[C@:23]([CH3:29])([CH2:24][CH2:25]1)[C@@H:13]([C@@H:14]([CH2:16][CH2:17][CH2:18][C:19]([O:21][CH3:22])=[O:20])[CH3:15])[CH2:12][CH2:11]2)=[CH:8][CH:7]=3.C[C:32]([CH3:35])([O-:34])[CH3:33].[K+].[CH2:37]([OH:41])[CH2:38][CH2:39][OH:40].C[Si](C=[N+]=[N-])(C)C>[Cl-].[Na+].O.O1CCCC1.CO.C(O)(=O)C.O>[OH:1][C@@H:2]1[C@@:27]2([CH3:28])[C:6](=[CH:7][CH:8]=[C:9]3[C@@H:26]2[CH2:25][CH2:24][C@@:23]2([CH3:29])[C@H:10]3[CH2:11][CH2:12][C@@H:13]2[C@@H:14]([CH2:16][CH2:17][CH2:18][C:19]([O:21][CH3:22])=[O:20])[CH3:15])[CH2:35][C@@H:32]([OH:34])[C@H:33]1[O:40][CH2:39][CH2:38][CH2:37][OH:41]

Participants

10

Reactant 4

HCID 104421,3-PropanediolHCID 167693TrimethylsilyldiazomethaneHCID 15858867HCID 15858867, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 15858861HCID 15858861, compoundYield 44%

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of 673 mg (1.63 mmol) of 1α,2α-epoxy-3β-hydroxy-20(R)-(3-methoxycarbonylpropyl)pregna-5,7-diene, 545 mg (4.86 mmol) of potassium t-butoxide and 9.38 ml (129 mmol) of 1,3-propanediol was stirred at 110° C. for 14 hours. 500 μl of water was added and the reaction mixture was stirred at 110° C. for 30 minutes. After cooling by means of an ice-water bath, 600 μl of acetic acid was added and the mixture was stirred for 10 minutes. Then, 1.3 ml of methanol, 4 ml of tetrahydrofuran and 6 ml (12.0 mmol) of trimethylsilyldiazomethane (2.0M solution in hexane) were added in this order and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into saturated brine and the product was extracted twice with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and the solvent was removed under reduced pressure. The residue was purified by silica gel flash column chromatography eluting with ethanol/dichloromethane (3:25) to give 348 mg (44%) of the titled compound as a pale yellow powder. ##STR8##

Workup

  1. stirringthe reaction mixture was stirred at 110° C. for 30 minutes
  2. temperatureAfter cooling by means of an ice-water bath
  3. stirringthe mixture was stirred for 10 minutes
  4. stirringthe mixture was stirred at room temperature for 1 hour
  5. extractionthe product was extracted twice with ethyl acetate
  6. washThe organic layer was washed with saturated brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customthe solvent was removed under reduced pressure
  10. customThe residue was purified by silica gel flash column chromatography
  11. washeluting with ethanol/dichloromethane (3:25)

Sources & evidence

ORD record
ord-45f1834acd624d6187702345accf5a05
Source dataset
uspto-grants-1999_03
Patent number
US05883271

Reaction notes

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