4-Toluenesulfonyl chloride → HCID 19376853、化合物

HRID 546167ノート

反応式

HRID 546167 の反応式
[CH2:1]([O:8][CH2:9][CH:10]([CH2:13][OH:14])[CH2:11]O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])CCC.CCCCCC.C1(C)C=CC(S(Cl)(=O)=O)=CC=1.CC(C)([O-])C.[K+]>O1CCCC1.O>[CH2:1]([O:8][CH2:9][CH:10]1[CH2:11][O:14][CH2:13]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

8

反応物 5

HCID 73974-Toluenesulfonyl chlorideHCID 8058HexaneHCID 102417822-benzyloxymethyl-propane-1,3-diolHCID 23665647Potassium tert-butoxideHCID 178418339Butyllithium

生成物 1

HCID 19376853HCID 19376853、化合物収率 51%

試薬・触媒・溶媒 2

HCID 962Water溶媒2 回HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
25 °C

実験手順

To a solution of 2-benzyloxymethyl-propane-1,3-diol (4.39 g, 22.36 mmol) in tetrahydrofuran (60 ml) stirred at −5° C., was added n-butyllithium in hexane (2.5 M, 11.18 ml, 27.96 mmol) and after 20 min, a solution of p-toluenesulfonyl chloride (5.12 g, 26.85 mmol) in tetrahydrofuran (20 ml) was added. The reaction was allowed to warm to 25° C. and then stirred for 2 h. To this solution was added water slowly and then extracted with ethyl acetate. The organics were dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was then dissolved in tert-butyl alcohol (90 ml) and potassium tert-butoxide (7.5 g, 66.83 mmol) was added, and the reaction was refluxed for 30 min and then stirred at 25° C. for 30 min. After such a time it was diluted with water (500 ml) and extracted with ether (2×250 ml). The extracts were combined and dried over magnesium sulfate, filtered and concentrated in vacuo. Purification on an AnaLogix Intelliflash system (120 g column, 20% ethyl acetate/hexanes to 30% ethyl acetate/hexanes) afforded 3-benzyloxymethyl-oxetane (2.02 g, 51%) as a light yellow oil: 1H NMR (300 MHz, CDCl3) δ ppm 3.19-3.32 (m, 1H, CH), 3.71 (d, J=6.9 Hz, 2H, OCH2), 4.42-4.48 (m, 2 H, 2×OCH of 2×OCH2), 4.55 (s, 2H, OCH2Ar), 4.77-4.83 (m, 2H, 2×OCH of 2×OCH2), 7.27-7.40 (m 5H, Ar).

後処理

  1. extractionextracted with ethyl acetate
  2. dry with materialThe organics were dried over magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. dissolutionThe residue was then dissolved in tert-butyl alcohol (90 ml)
  6. temperaturethe reaction was refluxed for 30 min
  7. stirringstirred at 25° C. for 30 min
  8. extractionextracted with ether (2×250 ml)
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customPurification on an AnaLogix Intelliflash system (120 g column, 20% ethyl acetate/hexanes to 30% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-d8c8494bbe944a5490a0af1db0116f3e
出典データセット
uspto-grants-2011_05
特許番号
US07935699B2

反応ノート

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