Diethylene Glycol Monomethyl Ether → Ethyl 2,5,8,11,14,17,20,23-octaoxanonacosan-29-oate

HRID 6623

Reaction equation

HRID 6623 reaction equation
[H-].[Na+].[CH3:3][O:4][CH2:5][CH2:6][O:7]CCO.[CH2:11]([O:13][C:14](=[O:42])[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][O:20][CH2:21][CH2:22][O:23][CH2:24][CH2:25][O:26][CH2:27][CH2:28][O:29][CH2:30][CH2:31][O:32][CH2:33][CH2:34][O:35][CH2:36][CH2:37]S(C)(=O)=O)[CH3:12]>C1(C)C=CC=CC=1>[CH2:11]([O:13][C:14](=[O:42])[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][O:20][CH2:21][CH2:22][O:23][CH2:24][CH2:25][O:26][CH2:27][CH2:28][O:29][CH2:30][CH2:31][O:32][CH2:33][CH2:34][O:35][CH2:36][CH2:37][O:7][CH2:6][CH2:5][O:4][CH3:3])[CH3:12]

Participants

5

Reactant 3

HCID 8134Diethylene Glycol Monomethyl EtherHCID 24758Sodium hydrideHCID 865870276-{2-[2-(2-{2-[2-(2-Methylsulfonylethoxy) ethoxy]ethoxy}-ethoxy)-ethoxy]-ethoxy}-hexanoic acid ethyl ester

Product 1

HCID 71366717Ethyl 2,5,8,11,14,17,20,23-octaoxanonacosan-29-oateYield 62.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent3×

Conditions

Temperature
0 °C

Procedure

NaH (88 mg of a 60% dispersion in oil, 2.2 mmol) was suspended in anhydrous toluene (3 ml) under N2 and chilled to 0° C. Non-polydispersed diethylene glycol monomethyl ether (0.26 ml, 0.26 g, 2.2 mmol) that had been dried via azeotropic distillation with toluene was added. The reaction mixture was allowed to warm to room temperature and stirred for four hours, during which time the cloudy grey suspension became clear and yellow and then turned brown. Mesylate 20 (0.50 g, 1.0 mmol) in 2.5 ml dry toluene was added. After stirring at room temperature over night, the reaction was quenched by the addition of 2 ml of methanol and the resultant solution was filtered through silica gel. The filtrate was concentrated in vacuo and the FAB MS: m/e 499 (M+H), 521 (M+Na). Additional purification by preparatory chromatography (silica gel, 19/3 chloroform/methanol) provided the non-polydispersed product as a clear yellow oil (0.302 g 57%). FAB MS: m/e 527 (M+H), 549 (M+Na).

Workup

  1. additionwas added
  2. temperatureto warm to room temperature
  3. stirringAfter stirring at room temperature over night
  4. customthe reaction was quenched by the addition of 2 ml of methanol
  5. filtrationthe resultant solution was filtered through silica gel
  6. concentrationThe filtrate was concentrated in vacuo
  7. customAdditional purification by preparatory chromatography (silica gel, 19/3 chloroform/methanol)

Sources & evidence

ORD record
ord-4fa6ce2833494a9795e9d24918fc4a33
Source dataset
uspto-grants-2006_08
Patent number
US07084114B2

Linked notes

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