Hydrochloric Acid → HCID 11543560, compound

HRID 884682Notes

Reaction equation

HRID 884682 reaction equation
[C:1]([C:4]1C=[CH:12][CH:11]=[C:10]2[C:5]=1[C:6](=[O:23])[C:7](C(=O)C)=[C:8]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[O:9]2)(=[O:3])C.C1C[O:27][CH2:26]C1.C([O-])([O-])=O.[K+].[K+].Cl>CO>[OH:3][C:1]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[O:9][C:8]([C:14]1[CH:15]=[CH:16][C:17]([CH2:26][OH:27])=[CH:18][CH:19]=1)=[CH:7][C:6]2=[O:23]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 11430Potassium CarbonateHCID 67114276HCID 67114276, compound

Product 1

HCID 11543560HCID 11543560, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

In a 100 mL round-bottomed flask fitted with condenser and magnetic stirrer were placed 2′-hydroxy-5′-acetoxyacetophenone (2.63 g, 13.54 mmol), 4-acetoxymethyl benzoic acid (2.63 g, 13.54 mmol) and pyridine (20 mL). POCl3 (2.07 g, 13.54 mmol) was added slowly on cooling. Then the reaction mixture was stirred for 24 h at rt under nitrogen. The reaction mixture was poured into ice water and extracted with EtOAc. The organic layer was washed with water, dried and concentrated to give product (3.0 g, 60%). A solution of this product (3.0 g, 8.10 mmol) in THF (50 mL), was added potassium t-butoxide (1.187 g, 9.72 mmol) and the reaction mixture was stirred for 24 h at rt under N2. The reaction mixture was poured into saturated aqueous solution of NH4Cl. The organic layer was separated, washed with water, dried and concentrated to give crude diketone (3.0 g, 99%). The mentioned diketone (3.0 g, 8.10 mmol) was taken into a mixture of 48% HCl (2 mL) and AcOH (25 mL) and heated at 100° C. for 1 h. The reaction mixture was cooled to rt, diluted with water and extracted with EtOAc. The organic layer was washed with water, brine, dried and concentrated to give the di-acetyl flavone (1.2 g, 74%). To a solution of the di-acetyl flavone (228 mg, 0.676 mmol) in methanol:THF (5 ml:5 mL), K2CO3 (112 mg, 0.811 mmol) was added and stirred for 2 h at rt, then the reaction mixture was neutralized by dilute HCl and extracted with EtOAc. The combined organic layers were washed with water, brine, dried and concentrated to give a crude product, which was purified by column chromatography using 2% MeOH in dichloromethane, to give 100 mg of 6-hydroxy-2-(4-hydroxymethylphenyl)chromen-4-one (50%). MS (ES) m/z: 269.90 (M+1), 268.91 (M); Mp. 262-265° C.

Workup

  1. extractionextracted with EtOAc
  2. washThe combined organic layers were washed with water, brine
  3. customdried
  4. concentrationconcentrated
  5. customto give a crude product, which
  6. customwas purified by column chromatography

Sources & evidence

ORD record
ord-6d8460702cab464c8e45b2e6e39b2f50
Source dataset
uspto-grants-2012_08
Patent number
US08242130B2

Reaction notes

Loading…