Ethanol → Bromo-PEG4-t-butyl ester

HRID 2083890ノート

反応式

HRID 2083890 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].C(O)C.C(Br)(Br)(Br)[Br:27].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl.C1(C)C=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:27])([CH3:4])([CH3:3])[CH3:2]

参加物

7

反応物 4

HCID 702EthanolHCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 11174684Hydroxy-PEG4-t-butyl ester

生成物 1

HCID 12082266Bromo-PEG4-t-butyl ester収率 47.5%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 6344Dichloromethane溶媒

実験手順

Alternatively, 1.61 g (5.03 mmol) of 9a was co-evaporated successively with 100% ethanol and toluene, then dried over anhydrous sodium sulfate and 4A molecular sieves in dichloromethane. The mixture was filtered and concentrated. To the dried compound (1.42 g) in 20 ml of dichloromethane was added 2.48 g of carbontetrabromide (CBr4, 7.47 mmol) and 1.50 g of triphenylphosphine (PPh3, 5.71 mmol). After stirring under an atmosphere of argon overnight, the reaction mixture was filtered through a silica gel bed, then concentrated and purified by silica gel chromatography. (EtOAc/Hexane Gradient starting at a ratio of 1:2 and changing to a ratio of 2:3) to yield 0.92 g of the 10a. (62%). Rf=0.64 (EtOAc); 1H NMR (CDCl3) 3.785 (t, 2H, J=6.3+6.3 Hz), 3.68 (t, 2H, J=6.5+6.5 Hz), 3.650 (m, 8H), 3.615 (m, 4H), 3.462 (t, 2H, J=6.3+6.4 Hz), 2.491 (t, 2H, J=6.5+6.5 Hz), 1.434 (s, 9H); 13C NMR 171.063, 80.656, 71.368, 70.831, 70.764, 70.706, 70.678, 70.545, 67.061, 36.431, 30.474, 28.263; MS m/z 408.74 (M+Na)+, 406.70, 405.70, 404.73.

後処理

  1. dry with materialdried over anhydrous sodium sulfate and 4A molecular sieves in dichloromethane
  2. filtrationThe mixture was filtered
  3. concentrationconcentrated
  4. filtrationthe reaction mixture was filtered through a silica gel bed
  5. concentrationconcentrated
  6. custompurified by silica gel chromatography

出典と根拠

ORDレコード
ord-b9175af2ab01437f8ad6dcf64f469d53
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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