Ethanol → HCID 12082266, compound

HRID 2083890Notes

Reaction equation

HRID 2083890 reaction equation
[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]

Participants

7

Reactant 4

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

Product 1

HCID 12082266HCID 12082266, compoundYield 47.5%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-b9175af2ab01437f8ad6dcf64f469d53
Source dataset
uspto-grants-2004_04
Patent number
US06716821B2

Reaction notes

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