Water → Deoxycholic Acid Impurity 69

HRID 1811520Notes

Reaction equation

HRID 1811520 reaction equation
[Cl-].[Cl-].C([Al+2])C.[C:6]([O:10][CH3:11])(=[O:9])[CH:7]=[CH2:8].[C:12]([O:15][C@@H:16]1[CH2:34][CH2:33][C@@:32]2([CH3:35])[C@H:18]([CH2:19][CH2:20][C@@H:21]3[C:31]2=[CH:30][CH2:29][C@@:28]2([CH3:36])[C@H:22]3[CH2:23][CH2:24]/[C:25]/2=[CH:26]/[CH3:27])[CH2:17]1)(=[O:14])[CH3:13].O>C(Cl)Cl>[C:12]([O:15][C@@H:16]1[CH2:34][CH2:33][C@@:32]2([CH3:35])[C@H:18]([CH2:19][CH2:20][C@@H:21]3[C:31]2=[CH:30][CH2:29][C@@:28]2([CH3:36])[C@H:22]3[CH2:23][CH:24]=[C:25]2[C@H:26]([CH3:27])[CH2:8][CH2:7][C:6]([O:10][CH3:11])=[O:9])[CH2:17]1)(=[O:14])[CH3:13]

Participants

6

Reactant 4

HCID 962WaterHCID 7294Methyl AcrylateHCID 16686341Ethyl aluminium dichlorideHCID 25145012(3R,5R,8S,10S,13S,14S,Z)-17-Ethylidene-10,13-dimethyl-2,3,4,5,6,7,8,10,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[A]phenanthren-3-YL acetate

Product 1

HCID 25145010Deoxycholic Acid Impurity 69Yield 70%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

Ethyl aluminum dichloride (14.2 mL, 25 mmol, 1.8M in toluene) was added to a solution of methyl acrylate (1.89 mL, 20 mmol) in DCM (60 mL) at 0° C. under inert atmosphere. The resulting solution was stirred for 15 min and then compound 1.6a (3 g, 8.7 mmol) was added. After stifling for an additional 20 min at 0° C., the temperature was raised to 25° C. and held there for a further 18 h. At this point the reaction was determined to be complete by TLC, then the mixture was poured into cold (0° C.) water (60 mL). The phases were separated and the aqueous layer was extracted with DCM (60 mL). The organic layers were combined and washed sequentially with water (50 mL) and saturated brine solution (100 mL). It was then dried over anhydrous Na2SO4 (5 g) and filtered. The filtrate was concentrated under vacuum, providing compound 1.7b (2.6 g, 70%).

Workup

  1. waitAfter stifling for an additional 20 min at 0° C.
  2. waitheld there for a further 18 h
  3. customThe phases were separated
  4. extractionthe aqueous layer was extracted with DCM (60 mL)
  5. washwashed sequentially with water (50 mL) and saturated brine solution (100 mL)
  6. dry with materialIt was then dried over anhydrous Na2SO4 (5 g)
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated under vacuum

Sources & evidence

ORD record
ord-cbc8788f00754f91a73072ec43e3283e
Source dataset
uspto-grants-2013_01
Patent number
US08362285B2

Reaction notes

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