Trifluoroacetic acid → HCID 10424224, compound

HRID 1446147Notes

Reaction equation

HRID 1446147 reaction equation
[BH4-].[Na+].FC(F)(F)C(O)=O.[CH2:10]([C@:12]12[CH2:20][CH:19]([OH:21])[C@@H:18]3[C@@H:22]4[C:27]([CH2:28][CH2:29][C@H:17]3[C@@H:16]1[CH2:15][CH2:14][C:13]2=[O:31])=[CH:26][C:25](=O)[CH2:24][CH2:23]4)[CH3:11].[OH-].[Na+]>ClCCl.C(O)(=O)C.O>[CH2:10]([C@:12]12[CH2:20][CH:19]([OH:21])[C@@H:18]3[C@@H:22]4[C:27]([CH2:28][CH2:29][C@H:17]3[C@@H:16]1[CH2:15][CH2:14][C:13]2=[O:31])=[CH:26][CH2:25][CH2:24][CH2:23]4)[CH3:11]

Participants

8

Reactant 4

HCID 6422Trifluoroacetic acidHCID 14798Sodium Hydroxide2×HCID 4311764Sodium borohydride2×HCID 59171130HCID 59171130, compound

Product 1

HCID 10424224HCID 10424224, compoundYield 110.4%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A suspension made of sodiumborohydride (152 g) in dichloromethane (0.60 liters) was added to a mixture of trifluoroacetic acid (1.13 liters) in acetic acid (1.13 liters) under stirring at a temperature of 0° C. in about 2 hours. At the end of the addition of the suspension of sodiumborohydride, a solution made of 13-ethyl-11-hydroxy-gon-4en-3,17-dione (201.00 g; 0.66 moles; compound XVIa) in dichloromethane (660 ml) was added to the reaction mixture under stirring at the temperature of 0° C. The reaction mixture was kept under stirring at a temperature of 20° C. for 20′ then it was cooled at the temperature of 0° C. and 4 liters of an aqueous admixture of sodium hydroxide were added (this solution was prepared from 1 liter of water and 3 liters of 30% sodium hydroxide). The reaction was then extracted with dichloromethane (3×2.5 liters), the organic extracts dehydrated on sodium sulfate, filtered and concentrated under vacuum to give 210.20 g of raw 13-ethyl-11-hydroxy-gon-4-en-17-one (compound XIVa). Such a crude may be further purified by silica gel chromatography (1/5 p/p) by eluting under a gradient of polarity, by using an admixture of toluene and ethyl acetate as mobile phase: by eluting with 9/1 toluene/ethyl acetate 144.67 g (0.50 moles; yields 76%) of pure compound XIVa were obtained, with the following analytical characteristics:

Workup

  1. additionwas added to the reaction mixture
  2. stirringunder stirring at the temperature of 0° C
  3. stirringunder stirring at a temperature of 20° C. for 20′ then it
  4. additionwere added (this solution
  5. extractionThe reaction was then extracted with dichloromethane (3×2.5 liters)
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-36f7071fa59a40849232c7f7cd3a880c
Source dataset
uspto-grants-2010_02
Patent number
US07667056B2

Reaction notes

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