Methanol → 2-Chloro-5-[(methylsulfinyl)methyl]pyridine

HRID 909365ノート

反応式

HRID 909365 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][S:9][CH3:10])=[CH:4][N:3]=1.ClC1C=CC=C(C(OO)=[O:19])C=1.CO>C(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][S:9]([CH3:10])=[O:19])=[CH:4][N:3]=1

参加物

5

反応物 3

HCID 887MethanolHCID 70297m-Chloroperbenzoic acidHCID 206703602-Chloro-5-[(methylthio)methyl]pyridine

生成物 1

HCID 592659452-Chloro-5-[(methylsulfinyl)methyl]pyridine収率 100.2%

試薬・触媒・溶媒 1

HCID 6212Chloroform溶媒2 回

実験手順

To a solution of 2-chloro-5-[(methylthio)methyl]pyridine (A) (7.60 g, 40 mmol) in chloroform (100 mL) cooled in ice-water bath was added a solution of 70-75% m-chloroperbenzoic acid (mCPBA, 10.51 g, ca 44 mmol) in chloroform (110 mL) over a period of 1.5 h under stirring. The stirring was continued for another 1 h at 0° C. Methanol (12 mL) was added to the mixture, which was then bubbled with ammonia gas to precipitate the benzoic acid and the extra mCPBA if any. TLC showed there was small amount of unreacted starting material in the reaction mixture. Most of the ammonium salt was removed by filtration. The filtrate was concentrated before it was loaded onto a Et3N-treated silica gel plug, which was eluted with 10% MeOH in CH2Cl2 to give 7.6 g of 2-chloro-5-[(methylsulfinyl)methyl]pyridine (B) in 92% yield as a colorless oil that turned into a white solid upon drying in vacuo (m.p. 72-74° C.). LC-MS (ELSD): mass calcd for C7H8ClNOS [M+H]+ 190.67. Found: 190.21.

後処理

  1. customwas then bubbled with ammonia gas
  2. customto precipitate the benzoic acid
  3. customMost of the ammonium salt was removed by filtration
  4. concentrationThe filtrate was concentrated before it
  5. additiontreated silica gel plug, which
  6. washwas eluted with 10% MeOH in CH2Cl2

出典と根拠

ORDレコード
ord-cabb0b1737e0453c86616a154e4706eb
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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