Acetone → (4-(Bromomethyl)-2,6-difluorophenyl)(methyl)sulfane

HRID 47647ノート

反応式

HRID 47647 の反応式
Cl[CH2:2][C:3]1[CH:4]=[C:5]([F:12])[C:6]([S:10][CH3:11])=[C:7]([F:9])[CH:8]=1.[Br-:13].[Li+].CC(C)=O.[Br-].[Na+]>O>[Br:13][CH2:2][C:3]1[CH:4]=[C:5]([F:12])[C:6]([S:10][CH3:11])=[C:7]([F:9])[CH:8]=1

参加物

6

反応物 4

HCID 180AcetoneHCID 82050Lithium Bromide2 回HCID 253881Sodium BromideHCID 227457405-(Chloromethyl)-1,3-difluoro-2-(methylthio)benzene

生成物 1

HCID 22746076(4-(Bromomethyl)-2,6-difluorophenyl)(methyl)sulfane

試薬・触媒・溶媒 1

HCID 962Water溶媒2 回

実験手順

A mixture of 5-(chloromethyl)-1,3-difluoro-2-(methylthio)benzene (21.3 g, 0.10 mol), lithium bromide (15 g, 0.17 mol), and acetone (200 mL) was heated and held at reflux for 18 hours. The cool mixture was poured into water and extracted with dichloromethane (1×200 mL, 2×50 mL). The combined extracts were dried using magnesium sulfate, and concentrated. The residue was dissolved in acetone (200 mL), lithium bromide (30 g, 0.34 mol) and sodium bromide (20 g, 0.19 mol) were added and the mixture heated and held at reflux for 42 hours. The mixture was cooled, added to water, and extracted with dichloromethane (1×150 mL, 1×50 mL). The combined extracts were washed with dilute sodium chloride, dried with magnesium sulfate, and concentrated. The 5-(bromomethyl)-1,3-difluoro-2-(methylthio)benzene was purified using silica gel chromatography using hexanes as a yellow solid (20.5 g, 80%). 1H NMR (CDCl3/400 MHz) 6.92-6.95 (m, 2H), 4.37 (s, 2H), 2.45 (s, 3H). HRMS m/z 251.9432 (M+, calcd 251.9420).

後処理

  1. temperaturewas heated
  2. temperatureat reflux for 18 hours
  3. extractionextracted with dichloromethane (1×200 mL, 2×50 mL)
  4. customThe combined extracts were dried
  5. concentrationconcentrated
  6. dissolutionThe residue was dissolved in acetone (200 mL)
  7. temperaturethe mixture heated
  8. temperatureat reflux for 42 hours
  9. temperatureThe mixture was cooled
  10. extractionextracted with dichloromethane (1×150 mL, 1×50 mL)
  11. washThe combined extracts were washed with dilute sodium chloride
  12. dry with materialdried with magnesium sulfate
  13. concentrationconcentrated
  14. customThe 5-(bromomethyl)-1,3-difluoro-2-(methylthio)benzene was purified

出典と根拠

ORDレコード
ord-f19f3fd62b044c8fb3dd821b2a9ffa5e
出典データセット
uspto-grants-2004_03
特許番号
US06699884B2

反応ノート

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