Water → Bromo-PEG4-t-butyl ester

HRID 2083889ノート

反応式

HRID 2083889 の反応式
[C:1]([O:5][C:6](=[O:22])[CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][O:15][CH2:16][CH2:17][O:18][CH2:19][CH2:20]O)([CH3:4])([CH3:3])[CH3:2].P(Br)(Br)[Br:24].O>N1C=CC=CC=1>[C:1]([O:5][C:6](=[O:22])[CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][O:15][CH2:16][CH2:17][O:18][CH2:19][CH2:20][Br:24])([CH3:4])([CH3:3])[CH3:2]

参加物

5

反応物 3

HCID 962WaterHCID 24614Phosphorus tribromideHCID 11174684Hydroxy-PEG4-t-butyl ester

生成物 1

HCID 12082266Bromo-PEG4-t-butyl ester収率 85.1%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒

実験手順

To a stirred solution of 9a (1.0 g, 3.11 mmol) in 1 mL of pyridine at 0° C. was slowly added phosphorus tribromide (0.116 mL, 1.22 mmol) via syringe (Bradshaw et al., J. Het. Chem., 27:347-349 (1990)). The solution was allowed to stir overnight, at which time TLC analysis indicated that the reaction was complete. Water (25 mL) was poured into the reaction vessel and the organics were extracted into methylene chloride (3×25 mL). The combined organic layers were washed with sodium bicarbonate (25 mL), followed by brine (25 mL), dried over magnesium sulfate, and the solvent was removed in vacuo. The residue was purified on silica gel using neat ethyl acetate as the eluant to give 400 mg (35% yield) of pure product 10a (FIG. 7). 1H NMR: 1.37 (s, 9H), 2.43 (t, 2H, J=6.4 Hz), 3.40 (t, 2H, J=6.4 Hz), 3.53-3.61 (m, 12H), 3.64 (t, 2H, J=6.4 Hz), 3.74 (t, 2H, J=6.4 Hz). 13C NMR: 27.90, 30.13, 36.06, 66.68, 70.17, 70.31, 70.32, 70.39, 70.46, 70.99, 80.22, 170.65.

後処理

  1. customat 0° C.
  2. extractionthe organics were extracted into methylene chloride (3×25 mL)
  3. washThe combined organic layers were washed with sodium bicarbonate (25 mL)
  4. dry with materialdried over magnesium sulfate
  5. customthe solvent was removed in vacuo
  6. customThe residue was purified on silica gel using neat ethyl acetate as the eluant

出典と根拠

ORDレコード
ord-838cf3f93d9249f39285c20d1d324d4a
出典データセット
uspto-grants-2004_04
特許番号
US06716821B2

反応ノート

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