Dimethylformamide → Ethyl 2-(6-bromo-2,3,4,5-tetramethoxybenzyl)-2-ethoxycarbonyl-6-(4-methoxycarbonylphenoxy)hexanoate

HRID 2268463Notes

Reaction equation

HRID 2268463 reaction equation
[H-].[Na+].CN(C=O)C.[CH2:8]([O:10][C:11]([CH:13]([CH2:19][CH2:20][CH2:21][CH2:22][O:23][C:24]1[CH:29]=[CH:28][C:27]([C:30]([O:32][CH3:33])=[O:31])=[CH:26][CH:25]=1)[C:14]([O:16][CH2:17][CH3:18])=[O:15])=[O:12])[CH3:9].[Br:34][C:35]1[C:40]([CH2:41]Br)=[C:39]([O:43][CH3:44])[C:38]([O:45][CH3:46])=[C:37]([O:47][CH3:48])[C:36]=1[O:49][CH3:50]>O>[Br:34][C:35]1[C:40]([CH2:41][C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])([CH2:19][CH2:20][CH2:21][CH2:22][O:23][C:24]2[CH:25]=[CH:26][C:27]([C:30]([O:32][CH3:33])=[O:31])=[CH:28][CH:29]=2)[C:11]([O:10][CH2:8][CH3:9])=[O:12])=[C:39]([O:43][CH3:44])[C:38]([O:45][CH3:46])=[C:37]([O:47][CH3:48])[C:36]=1[O:49][CH3:50]

Participants

6

Reactant 4

HCID 6228Dimethylformamide2×HCID 24758Sodium hydrideHCID 18348545Ethyl 2-ethoxycarbonyl-6-(4-methoxycarbonylphenoxy)hexanoateHCID 183486201-Bromo-6-bromomethyl-2,3,4,5-tetramethoxybenzene

Product 1

HCID 18348654Ethyl 2-(6-bromo-2,3,4,5-tetramethoxybenzyl)-2-ethoxycarbonyl-6-(4-methoxycarbonylphenoxy)hexanoateYield 98.2%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Sodium hydride (60% oily, 1.02 g, 25.6 mmols) was added to a DMF (80 ml) solution of ethyl 2-ethoxycarbonyl-6-(4-methoxycarbonylphenoxy)hexanoate (8.55 g, 23.3 mmols), with cooling with ice, then allowed to warm to room temperature, and stirred for 30 minutes. Next, a DMF (10 ml) solution of 1-bromo-6-bromomethyl-2,3,4,5-tetramethoxybenzene (9.47 g, 25.6 mmols) was dropwise added thereto at room temperature, and stirred for 6 hours. Water was added to the reaction mixture, which was then extracted with diethyl ether. The organic layer was washed with water and a saturated aqueous sodium chloride solution, and then dried. The solvent was evaporated out in vacuo, and the resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=20:1 to 5:1) to obtain the entitled compound (15.0 g) as an oil.

Workup

  1. temperaturewith cooling with ice
  2. stirringat room temperature, and stirred for 6 hours
  3. extractionwas then extracted with diethyl ether
  4. washThe organic layer was washed with water
  5. dry with materiala saturated aqueous sodium chloride solution, and then dried
  6. customThe solvent was evaporated out in vacuo
  7. customthe resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=20:1 to 5:1)

Sources & evidence

ORD record
ord-deead60716134b61b23c283c9755ac10
Source dataset
uspto-grants-2001_12
Patent number
US06326369B1

Reaction notes

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