2-Chloro-5-(chloromethyl)pyridine → 2-Chloro-5-[(methylthio)methyl]pyridine

HRID 909364ノート

反応式

HRID 909364 の反応式
Cl[CH2:2][C:3]1[CH:4]=[CH:5][C:6]([Cl:9])=[N:7][CH:8]=1.[CH3:10][S-:11].[Na+]>C(O)C>[Cl:9][C:6]1[CH:5]=[CH:4][C:3]([CH2:2][S:11][CH3:10])=[CH:8][N:7]=1

参加物

4

反応物 2

HCID 1554792-Chloro-5-(chloromethyl)pyridineHCID 4378561Sodium methanethiolate

生成物 1

HCID 206703602-Chloro-5-[(methylthio)methyl]pyridine収率 94%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒2 回

実験手順

A solution of 5-chloromethyl-2-chloropyridine (8.1 g, 50 mmol) in ethanol (50 mL) was added to a suspension of sodium thiomethoxide solid (4.2 g, 60 mmol) in 100 mL ethanol under stirring. An exothermic reaction was observed during the addition and the mixture was then stirred at room temperature overnight. The solvent ethanol was removed under reduced pressure and the residue was re-dissolved in ether-EtOAc solvent and mixed with brine. The two phases were separated and the organic layer was dried over anhydrous Na2SO4, filtered, concentrated and purified by eluting through a silica gel plug with 40% EtOAc in hexane to give 8.14 g of 2-chloro-5-[(methylthio)methyl]pyridine (A) as a colorless oil in 94% yield. The product was analytically pure and directly used for the next step reaction. 1H NMR (300 MHz, CDCl3) δ 8.28 (dd, 1H), 7.65 (dd, 1H), 7.30 (d, 1H), 3.63 (s, 2H), 2.00 (s, 3H).

後処理

  1. customAn exothermic reaction
  2. additionwas observed during the addition
  3. stirringthe mixture was then stirred at room temperature overnight
  4. customThe solvent ethanol was removed under reduced pressure
  5. dissolutionthe residue was re-dissolved in ether-EtOAc solvent
  6. additionmixed with brine
  7. customThe two phases were separated
  8. dry with materialthe organic layer was dried over anhydrous Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. custompurified
  12. washby eluting through a silica gel plug with 40% EtOAc in hexane

出典と根拠

ORDレコード
ord-9e4079a88de8459cb462ed8d94158831
出典データセット
uspto-grants-2011_09
特許番号
US08017788B2

反応ノート

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