Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1) → HCID 77230948, compound

HRID 571080Notes

Reaction equation

HRID 571080 reaction equation
[C:1]([O:4][C:5]([C:9](=[O:19])[CH2:10][C:11](=[O:18])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[CH:6]OC)(=[O:3])[CH3:2].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1>C1(C)C=CC=CC=1>[C:1]([O:4][C:5]1[C:9](=[O:19])[CH:10]=[C:11]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[O:18][CH:6]=1)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 67418524HCID 67418524, compound

Product 1

HCID 77230948HCID 77230948, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 545 mg (3.5 mmol) of 1-methoxy-3-oxobut-1-en-2-yl acetate in THF (14.2 mL) at −78° C. was added LHMDS (3.45 mL of a 1 M solution in toluene) dropwise. After stirring for min at −78° C., the reaction mixture was treated with 0.4 mL (3.5 mmol) of benzoyl chloride dropwise, then removed from the cold bath and allowed to warm to room temperature and continue stirring for 18 h. The reaction was quenched with 10 mL 10% aq HCl and extracted with diethyl ether (3×10 mL). The organic fractions were combined, washed with sat. aq. NaCl, dried (Na2SO4), and concentrated under reduced pressure to provide 1-methoxy-3,5-dioxo-5-phenylpent-1-en-2-yl acetate which was used the subsequent step without further purification. To a solution of crude 1-methoxy-3,5-dioxo-5-phenylpent-1-en-2-yl acetate (3.5 mmol) in toluene (35 mL) was added pyridinium p-toluenesulfonate (130 mg, 0.5 mmol). The reaction mixture was heated at reflux under a nitrogen atmosphere for 1 h before being cooled and concentrated under reduced pressure and purified by flash chromatography (80 g SiO2, 0-100% ethyl acetate/hexanes gradient elution) to provide 4-oxo-6-phenyl-4H-pyran-3-yl acetate. LC/MS (M+H)+ 231.

Workup

  1. customwithout further purification
  2. temperatureThe reaction mixture was heated
  3. temperatureat reflux under a nitrogen atmosphere for 1 h
  4. temperaturebefore being cooled
  5. concentrationconcentrated under reduced pressure
  6. custompurified by flash chromatography (80 g SiO2, 0-100% ethyl acetate/hexanes gradient elution)

Sources & evidence

ORD record
ord-8fcc84b0be4a42ba9bf747b6cba260bd
Source dataset
uspto-grants-2015_05
Patent number
US09024032B2

Reaction notes

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