Tetramethyltin → HCID 178498939, compound

HRID 1423912Notes

Reaction equation

HRID 1423912 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].[CH3:18][Sn](C)(C)C>CN(C=O)C.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]([CH3:18])[CH:9]=2)=[O:4]

Participants

5

Reactant 2

HCID 11661TetramethyltinHCID 178498916HCID 178498916, compound

Product 1

HCID 178498939HCID 178498939, compoundYield 68.3%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
122.5 °C

Procedure

To a mixture of 7-bromo-4-hydroxy-2-oxo-2H-thiochromene-3-carboxylic acid methyl ester (Example 5e) (150 mg, 0.48 mmol) in DMF was added tetramethyltin (254 mg, 1.43 mmol) and PdCl2(PPh3)2 (17 mg, 0.024 mmol). The resulting mixture was purged with nitrogen gas for 20 seconds and heated in a 120-125° C. oil bath for 1 h. The reaction mixture was diluted with water (15 mL) and the suspended black solid was filtered off. The clear filtrate was acidified to pH 4 using 1 N HCl and extracted with EtOAc (2×). The combined organic layers were washed with brine, dried over MgSO4, filtered and concentrated. The crude product was triturated with MeOH (1 mL) and the solid collected to provide 4-hydroxy-7-methyl-2-oxo-2H-thiochromene-3-carboxylic acid methyl ester (82 mg). 1H NMR (200 MHz, CDCl3): δ (ppm)=15.20 (s, 1H), 8.23 (d, J=8.5 Hz, 1H), 7.17 (m, 2H), 4.00 (s, 3H), 2.44 (s, 3H).

Workup

  1. customThe resulting mixture was purged with nitrogen gas for 20 seconds
  2. additionThe reaction mixture was diluted with water (15 mL)
  3. filtrationthe suspended black solid was filtered off
  4. extractionextracted with EtOAc (2×)
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was triturated with MeOH (1 mL)
  10. customthe solid collected

Sources & evidence

ORD record
ord-34f2f693a7db443196a8558ed60c9885
Source dataset
uspto-grants-2015_01
Patent number
US08927591B2

Reaction notes

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