Ethanol → HCID 59331612, compound

HRID 1882118Notes

Reaction equation

HRID 1882118 reaction equation
[CH:1]1([S:4]([C:7]2[CH:12]=[CH:11][C:10]([CH:13]([CH2:18][CH:19]3[CH2:24][CH2:23][O:22][CH2:21][CH2:20]3)[C:14](=O)[CH:15]=[CH2:16])=[CH:9][CH:8]=2)(=[O:6])=[O:5])[CH2:3][CH2:2]1.C(O)C.O1CCCC1.[C:33]([O:37][CH2:38][CH3:39])(=[O:36])[CH:34]=O.C([N:42](CC)CC)C>[Cl-].C([N+]1C(C)=C(CCO)SC=1)C1C=CC=CC=1.C(OCC)(=O)C>[CH:1]1([S:4]([C:7]2[CH:8]=[CH:9][C:10]([CH:13]([C:14]3[NH:42][C:34]([C:33]([O:37][CH2:38][CH3:39])=[O:36])=[CH:16][CH:15]=3)[CH2:18][CH:19]3[CH2:20][CH2:21][O:22][CH2:23][CH2:24]3)=[CH:11][CH:12]=2)(=[O:6])=[O:5])[CH2:2][CH2:3]1

Participants

8

Reactant 5

HCID 702EthanolHCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 70211Ethyl oxoacetateHCID 593312584-[4-(cyclopropylsulfonyl)phenyl]-5-(tetrahydro-2H-pyran-4-yl)pent-1-en-3-one

Product 1

HCID 59331612HCID 59331612, compoundYield 34%

Reagents, catalysts & solvents 2

HCID 28333523-Benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chlorideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 4-[4-(cyclopropylsulfonyl)phenyl]-5-(tetrahydro-2H-pyran-4-yl)pent-1-en-3-one (500 mg) in a mixed solvent of ethanol (15 mL) and tetrahydrofuran (5 mL) were added ethyl glyoxylate (polymer type, 47% toluene solution) (623 mg), 3-benzyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiazol-3-ium chloride (43 mg) and triethylamine (86 μL), and the mixture was heated under reflux under argon atmosphere for 30% min. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate and washed with water. The ethyl acetate layer was washed with saturated brine, dried (MgSO4) and concentrated. The residue was dissolved in acetic acid (5 mL), ammonium acetate (1.7 g) was added, and the mixture was stirred at 110° C. for 30 min. After cooling to room temperature, the mixture was neutralized with saturated aqueous sodium hydrogen carbonate solution. The reaction mixture was diluted with ethyl acetate and washed with water. The ethyl acetate layer was washed with saturated brine, dried (MgSO4) and concentrated. The residue was subjected to silica gel column chromatography, and the title compound (210 mg, yield 34%) was obtained as a pale-yellow amorphous solid from a fraction eluted with hexane-ethyl acetate (1:1, volume ratio). MS: 432 (MH+).

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux under argon atmosphere for 30% min
  3. washwashed with water
  4. washThe ethyl acetate layer was washed with saturated brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. dissolutionThe residue was dissolved in acetic acid (5 mL)
  8. additionammonium acetate (1.7 g) was added
  9. temperatureAfter cooling to room temperature
  10. additionThe reaction mixture was diluted with ethyl acetate
  11. washwashed with water
  12. washThe ethyl acetate layer was washed with saturated brine
  13. dry with materialdried (MgSO4)
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-41c915cd915d46029184ed6fa3d20542
Source dataset
uspto-grants-2012_11
Patent number
US08318746B2

Reaction notes

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