Sodium Sulfate → (4-((Triisopropylsilyl)oxy)phenyl)methanol

HRID 2400544ノート

反応式

HRID 2400544 の反応式
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:7][CH:8]([Si:10]([CH:26]([CH3:28])[CH3:27])([CH:23]([CH3:25])[CH3:24])[O:11][C:12]1[CH:22]=[CH:21][C:15]([C:16](OCC)=[O:17])=[CH:14][CH:13]=1)[CH3:9].S([O-])([O-])(=O)=O.[Na+].[Na+]>C(OCC)C>[CH3:25][CH:23]([Si:10]([CH:26]([CH3:28])[CH3:27])([CH:8]([CH3:9])[CH3:7])[O:11][C:12]1[CH:22]=[CH:21][C:15]([CH2:16][OH:17])=[CH:14][CH:13]=1)[CH3:24]

参加物

5

反応物 3

HCID 24436Sodium SulfateHCID 21226445Aluminium lithium hydrideHCID 59504619Ethyl 4-{[tris(1-methylethyl)silyl]oxy}benzoate

生成物 1

HCID 59504706(4-((Triisopropylsilyl)oxy)phenyl)methanol

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
0 °C

実験手順

To 75 mL of dry diethyl ether was added a solution of lithium aluminium hydride (4M in diethyl ether, 14 mL, 55.8 mmol), and the solution was cooled to 0° C. A solution of ethyl 4-{[tris(1-methylethyl)silyl]oxy}benzoate (Step 1, 9.0 g, 27.9 mmol) in dry diethyl ether (90 mL) was added dropwise, maintaining the temperature below 5-10° C. After the addition was completed, stirring of the reaction mixture was continued for 1 h at 0° C. Then, still at the same temperature, a saturated aqueous solution of sodium sulfate (60 mL) was added with caution. After warming to rt, the precipitate which had formed was removed by filtration, and the residue was washed with diethyl ether. The organic layer was separated from the filtrate, and the aqueous layer was extracted with diethyl ether. The combined organic layers were washed with water and brine and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed in vacuo. The crude product thus obtained was purified by MPLC (silica, cyclohexane/ethyl acetate 5:1→1:1) to afford the title compound in pure form (7.38 g, 94%): 1H NMR (400 MHz, CDCl3) δ 7.21 (d, 2H), 6.87 (d, 2H), 4.60 (d, 2H), 1.56 (t, 1H), 1.23 (m, 1H), 1.10 (d, 18H); EI-MS m/z 280 (M)+; HPLC RT (Method H) 5.33 min.

後処理

  1. temperaturemaintaining the temperature below 5-10° C
  2. additionAfter the addition
  3. temperatureAfter warming to rt
  4. customthe precipitate which had formed
  5. customwas removed by filtration
  6. washthe residue was washed with diethyl ether
  7. customThe organic layer was separated from the filtrate
  8. extractionthe aqueous layer was extracted with diethyl ether
  9. washThe combined organic layers were washed with water and brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. filtrationAfter filtration
  12. customthe solvent was removed in vacuo
  13. customThe crude product thus obtained
  14. customwas purified by MPLC (silica, cyclohexane/ethyl acetate 5:1→1:1)

出典と根拠

ORDレコード
ord-77a1c7f9439045299ab26c554edb345f
出典データセット
uspto-grants-2014_08
特許番号
US08796253B2

反応ノート

読み込み中…