Hydrochloric Acid → HCID 178498937, compound

HRID 1746201Notes

Reaction equation

HRID 1746201 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:6](=[O:17])[S:7][C:8]2[C:13]([C:14]=1[OH:15])=[CH:12][CH:11]=[C:10](Br)[CH:9]=2)=[O:4].[CH2:18]([B-](F)(F)F)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[K+].C([O-])([O-])=O.[Cs+].[Cs+].Cl>C1COCC1.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[C:6](=[O:17])[S:7][C:8]2[C:13]([C:14]=1[OH:15])=[CH:12][CH:11]=[C:10]([CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH:9]=2)=[O:4]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 10796Cesium carbonateHCID 23692459Potassium benzyltrifluoroboranuideHCID 178498916HCID 178498916, compound

Product 1

HCID 178498937HCID 178498937, compoundYield 43.3%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 7-bromo-4-hydroxy-2-oxo-2H-thiochromene-3-carboxylic acid methyl ester (Example 5 e) (220 mg, 0.70 mmol) in THF (8 mL) was added potassium benzyltrifluoroborate (138 mg, 0.70 mmol), Cs2CO3 (682 mg, 2.09 mmol), PdCl2(PPh3)2 (49 mg, 0.07 mmol) and then water (2 mL). The resulting mixture was refluxed overnight (18 h). After cooling, the reaction mixture was diluted with water (75 mL) and acidified using 1 N HCl to pH 4. The precipitate was collected, rinsed with water and the solid dissolved in CH2Cl2. The CH2Cl2 solution was dried over MgSO4, filtered, concentrated and the crude product purified by silica gel chromatography (5%-100% EtOAc/CH2Cl2) to provide 7-benzyl-4-hydroxy-2-oxo-2H-thiochromene-3-carboxylic acid methyl ester (99 mg). 1H NMR (200 MHz, CDCl3): δ (ppm)=15.2 (s, 1H), 8.25 (d, J=8.2 Hz, 1H), 7.36-7.16 (m, 7H), 4.04 (s, 2H), 4.00 (s, 3H).

Workup

  1. temperatureThe resulting mixture was refluxed overnight (18 h)
  2. temperatureAfter cooling
  3. customThe precipitate was collected
  4. washrinsed with water
  5. dissolutionthe solid dissolved in CH2Cl2
  6. dry with materialThe CH2Cl2 solution was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customthe crude product purified by silica gel chromatography (5%-100% EtOAc/CH2Cl2)

Sources & evidence

ORD record
ord-42bccdc23f0845308258874d7ca93711
Source dataset
uspto-grants-2015_10
Patent number
US09149476B2

Reaction notes

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