tert-Butylsulfinamide, (R)-(+)- → HCID 90301392、化合物

HRID 627647ノート

反応式

HRID 627647 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([C:9](=O)[CH3:10])[C:5]([F:8])=[N:6][CH:7]=1.[CH3:12][C:13]([S@:16]([NH2:18])=[O:17])([CH3:15])[CH3:14]>C1COCC1.[Cl-].[Na+].O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:3]=[C:4](/[C:9](=[N:18]\[S@@:16]([C:13]([CH3:15])([CH3:14])[CH3:12])=[O:17])/[CH3:10])[C:5]([F:8])=[N:6][CH:7]=1

参加物

6

反応物 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 401519061-(5-Bromo-2-fluoropyridin-3-yl)ethan-1-one

生成物 1

HCID 90301392HCID 90301392、化合物収率 99%

試薬・触媒・溶媒 3

HCID 76524Titanium tetraethoxide触媒HCID 8028Tetrahydrofuran溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

A mixture of 1-(5-bromo-2-fluoropyridin-3-yl)ethanone (11 g, 51 mmol), (R)-2-methylpropane-2-sulfinamide (12.2 g, 101 mmol) and titanium (IV) ethoxide (26.1 mL, 126 mmol) in THF (100 mL) was heated to reflux for 2 h. The mixture was cooled to room temperature, brine was added and the mixture was stirred for 10 min. The suspension was filtered through silica gel. The organic phase was separated and the aqueous phase was extracted with EtOAc. The combined organic extracts were washed with brine, dried over Na2SO4, filtered, and concentrated. Purification by flash column chromatography on silica gel (eluted with 0-20% EtOAc/hexanes) gave (R,Z)—N-(1-(5-bromo-2-fluoropyridin-3-yl)ethylidene)-2-methylpropane-2-sulfinamide (16 g, 50 mmol, 99% yield) as a bright yellow oil. LC/MS (ESI) m/z=321 (M+H).

後処理

  1. temperaturewas heated
  2. temperatureto reflux for 2 h
  3. filtrationThe suspension was filtered through silica gel
  4. customThe organic phase was separated
  5. extractionthe aqueous phase was extracted with EtOAc
  6. washThe combined organic extracts were washed with brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by flash column chromatography on silica gel (eluted with 0-20% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-6986b2dbdb43488c8b238cf07c34d92d
出典データセット
uspto-grants-2016_04
特許番号
US09309263B2

反応ノート

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