Hydrochloric Acid → HCID 76594466, compound

HRID 1867638Notes

Reaction equation

HRID 1867638 reaction equation
[F:1][C:2]([F:32])([F:31])[C:3]1[CH:4]=[C:5]([CH:24]=[C:25]([C:27]([F:30])([F:29])[F:28])[CH:26]=1)[CH2:6][O:7][CH2:8][C:9]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[CH:18]1OCCC[O:19]1)=[CH:10][CH3:11].Cl.[BH4-].[Na+]>CC(C)=O.O>[F:1][C:2]([F:31])([F:32])[C:3]1[CH:4]=[C:5]([CH:24]=[C:25]([C:27]([F:29])([F:28])[F:30])[CH:26]=1)[CH2:6][O:7][CH2:8][C:9]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[CH2:18][OH:19])=[CH:10][CH3:11]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 4311764Sodium borohydrideHCID 76594467HCID 76594467, compound

Product 1

HCID 76594466HCID 76594466, compound

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 2-(2-(1-(3,5-bis(trifluoromethyl)benzyloxy)but-2-en-2-yl)phenyl)-1,3-dioxane (1.75 g, 3.8 mmol) in acetone (100 mL) and water (5 mL) at room temperature was added concentrated hydrochloric acid (0.4 mL). The resulting solution was stirred for 1.5 h. The reaction was quenched by the addition of saturated sodium bicarbonate, and poured into pentane. The organics were washed with water (2×), then brine, dried over magnesium sulfate, and concentrated. The crude residue was dissolved in ethanol (20 mL), cooled to 0° C., and treated with sodium borohydride (0.14 g, 3.8 mmol). After 5 min, the ice bath was removed and stirring continued for 30 min. The mixture was recooled to 0° C., and quenched by addition of saturated ammonium chloride. The mixture was extracted with ether, washed with water (2×), then brine, dried over magnesium sulfate, and concentrated. Column chromatography (5%-->25% EtOAc/Hex) gave 1.22 g (79%) as colorless oil and as a mixture of E- and Z-isomers. 1H-NMR (mixture, CDCl3, 300 MHz) δ 7.76 (s, 1H), 7.62 (s, 1.5H), 7.59 (s, 0.4H), 7.20-7.50 (m, 3.3H), 7.13 (d, J=7.0 Hz, 0.2H), 7.05 (m, 0.8H), 5.96 (q, J=6.7 Hz, 0.8H), 5.72 (q, J=7.0 Hz, 0.2H), 4.05-4.80 (m, 6.2H), 2.65 (m, 1H), 1.85 (d, J=7.0 Hz, 0.6H), 1.66 (bs, 0.4H), 1.47 (d, J=6.7 Hz, 2.4H).

Workup

  1. customThe reaction was quenched by the addition of saturated sodium bicarbonate
  2. additionpoured into pentane
  3. washThe organics were washed with water (2×)
  4. dry with materialbrine, dried over magnesium sulfate
  5. concentrationconcentrated
  6. dissolutionThe crude residue was dissolved in ethanol (20 mL)
  7. waitAfter 5 min
  8. customthe ice bath was removed
  9. stirringstirring
  10. waitcontinued for 30 min
  11. customwas recooled to 0° C.
  12. customquenched by addition of saturated ammonium chloride
  13. extractionThe mixture was extracted with ether
  14. washwashed with water (2×)
  15. dry with materialbrine, dried over magnesium sulfate
  16. concentrationconcentrated
  17. customColumn chromatography (5%-->25% EtOAc/Hex) gave 1.22 g (79%) as colorless oil
  18. additionas a mixture of E- and Z-isomers

Sources & evidence

ORD record
ord-58eca3eac9204e70b3dcf001c0f9c64d
Source dataset
uspto-grants-2009_12
Patent number
US07632861B2

Reaction notes

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