Tetramethyltin → HCID 178498939、化合物

HRID 1746186ノート

反応式

HRID 1746186 の反応式
[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]

参加物

5

反応物 2

HCID 11661TetramethyltinHCID 178498916HCID 178498916、化合物

生成物 1

HCID 178498939HCID 178498939、化合物収率 68.3%

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
122.5 °C

実験手順

To a mixture of 7-bromo-4-hydroxy-2-oxo-2H-thiochromene-3-carboxylic acid methyl ester (Example 5 e) (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).

後処理

  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

出典と根拠

ORDレコード
ord-0931c1500039490b832cc54a086f42a0
出典データセット
uspto-grants-2015_10
特許番号
US09149476B2

反応ノート

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