tert-Butylsulfinamide, (R)-(+)- → N-(7-bromo-3-chloro-1-fluoro-5H-chromeno[2,3-c]pyridin-5-ylidene)-2-methylpropane-2-sulfinamide

HRID 455576ノート

反応式

HRID 455576 の反応式
[Br:1][C:2]1[CH:3]=[C:4]2[C:15](=[CH:16][CH:17]=1)[O:14][C:7]1[C:8]([F:13])=[N:9][C:10]([Cl:12])=[CH:11][C:6]=1[C:5]2=O.[CH3:19][C:20]([S@:23]([NH2:25])=[O:24])([CH3:22])[CH3:21]>C1COCC1.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:3]=[C:4]2[C:15](=[CH:16][CH:17]=1)[O:14][C:7]1[C:8]([F:13])=[N:9][C:10]([Cl:12])=[CH:11][C:6]=1[C:5]2=[N:25][S:23]([C:20]([CH3:22])([CH3:21])[CH3:19])=[O:24]

参加物

5

反応物 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-3 回HCID 574756427-bromo-3-chloro-1-fluoro-5H-chromeno[2,3-c]pyridin-5-one

生成物 1

HCID 86658361N-(7-bromo-3-chloro-1-fluoro-5H-chromeno[2,3-c]pyridin-5-ylidene)-2-methylpropane-2-sulfinamide収率 57.1%

試薬・触媒・溶媒 2

HCID 76524Titanium tetraethoxide触媒3 回HCID 8028Tetrahydrofuran溶媒

反応条件

温度
70 °C

実験手順

A suspension of 7-bromo-3-chloro-1-fluoro-5H-chromeno[2,3-c]pyridin-5-one (20 g, 60.9 mmol), (R)-2-methyl-2-propanesulfinamide (14.76 g, 122 mmol), and titanium (IV) ethoxide (25.2 mL, 122 mmol) in THF (250 mL) was heated to 70° C. for 24 h. Additional (R)-2-methyl-2-propanesulfinamide (1.0 equiv) and titanium (IV) ethoxide (1.0 equiv) were added and the reaction mixture was heated for additional 24 h. Additional (R)-2-methyl-2-propanesulfinamide (1.0 equiv) and titanium (IV) ethoxide (1.0 equiv) were added and the reaction mixture was heated for additional 8 h. The reaction mixture was quenched with brine (150 mL). The resulting suspension was filtered through celite, and the filter cake was washed with EtOAc. The filtrate was washed with brine, dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by chromatography (100% hexanes) to afford racemic N-(7-bromo-3-chloro-1-fluoro-5H-chromeno[2,3-c]pyridin-5-ylidene)-2-methylpropane-2-sulfinamide as an orange solid (15 g, 34.7 mmol, 57.1% yield).

後処理

  1. temperaturethe reaction mixture was heated for additional 24 h
  2. temperaturethe reaction mixture was heated for additional 8 h
  3. customThe reaction mixture was quenched with brine (150 mL)
  4. filtrationThe resulting suspension was filtered through celite
  5. washthe filter cake was washed with EtOAc
  6. washThe filtrate was washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by chromatography (100% hexanes)

出典と根拠

ORDレコード
ord-b4481218f09e4b129912b6161cabacdd
出典データセット
uspto-grants-2013_07
特許番号
US08497264B2

反応ノート

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