4-Toluenesulfonyl chloride → [2-Methyl-7,8-dihydro[1,4]dioxino[2,3-g][1,3]benzoxazol-8-yl]methyl 4-methylbenzenesulfonate

HRID 1454309

反応式

HRID 1454309 の反応式
[CH3:1][C:2]1[O:3][C:4]2[C:10]3[O:11][C@@H:12]([CH2:15][OH:16])[CH2:13][O:14][C:9]=3[CH:8]=[CH:7][C:5]=2[N:6]=1.[C:17]1([CH3:27])[CH:22]=[CH:21][C:20]([S:23](Cl)(=[O:25])=[O:24])=[CH:19][CH:18]=1.C(N(C(C)C)CC)(C)C>C(Cl)Cl.CN(C)C1C=CN=CC=1>[CH3:27][C:17]1[CH:22]=[CH:21][C:20]([S:23]([O:16][CH2:15][CH:12]2[CH2:13][O:14][C:9]3[CH:8]=[CH:7][C:5]4[N:6]=[C:2]([CH3:1])[O:3][C:4]=4[C:10]=3[O:11]2)(=[O:25])=[O:24])=[CH:19][CH:18]=1

参加物

6

反応物 3

HCID 73974-Toluenesulfonyl chlorideHCID 81531DiisopropylethylamineHCID 69017866[(8S)-2-methyl-7,8-dihydro[1,4]dioxino[2,3-g)[1,3]benzoxazol-8-yl]methanol

生成物 1

HCID 11268854[2-Methyl-7,8-dihydro[1,4]dioxino[2,3-g][1,3]benzoxazol-8-yl]methyl 4-methylbenzenesulfonate

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 6344Dichloromethane溶媒3 回

実験手順

To a solution of [(8S)-2-methyl-7,8-dihydro[1,4]dioxino[2,3-g][1,3]benzoxazol-8-yl]methanol (1.80 g, 8.14 mmole) in methylene chloride (100 mL) was added p-toluenesulfonyl chloride (3.90 g, 20.4 mmole). The mixture was cooled in an ice bath and a solution of diisopropylethylamine (3.55 mL, 20.4 mmole) in methylene chloride (20 mL) was then added dropwise, followed by 4-dimethylaminopyridine (0.65 g, 5.30 mmole). The solution was allowed to warm to room temperature and was stirred under nitrogen overnight. The reaction was diluted to 500 mL in volume with methylene chloride, then washed with aqueous 2 N HCl (200 mL), with saturated aqueous sodium bicarbonate (200 mL), and with brine (150 mL), dried over magnesium sulfate, filtered and evaporated in vacuum to a yellow oil. The crude oil was column chromatographed on silica gel using methylene chloride to remove impurities and 3% methanol/methylene chloride to elute the (R)-enantiomer of the title compound, which becomes a white solid under vacuum (2.56 g, 84%), m.p. 123° C. MS (ESI) m/z 376 (M+H)+.

後処理

  1. temperatureThe mixture was cooled in an ice bath
  2. washwashed with aqueous 2 N HCl (200 mL), with saturated aqueous sodium bicarbonate (200 mL)
  3. dry with materialwith brine (150 mL), dried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated in vacuum to a yellow oil
  6. customchromatographed on silica gel
  7. customto remove impurities and 3% methanol/methylene chloride
  8. washto elute the (R)-enantiomer of the title compound, which

出典と根拠

ORDレコード
ord-8a8ad043fd774ae38535c6d47d31480d
出典データセット
uspto-grants-2009_01
特許番号
US07479500B2

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