Hydrochloric Acid → Diethyl 2,2-bis(6-benzyloxyhexyl)malonate

HRID 1289382Notes

Reaction equation

HRID 1289382 reaction equation
[H-].[Na+].[CH2:3]([O:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH:17]([C:23]([O:25][CH2:26][CH3:27])=[O:24])[C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.Br[CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][O:35][CH2:36][C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1.Cl>CN(C)C=O>[CH2:3]([O:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][C:17]([CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][O:35][CH2:36][C:37]1[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=1)([C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:23]([O:25][CH2:26][CH3:27])=[O:24])[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 2784764Benzyl 6-Bromohexyl EtherHCID 10383239Diethyl 2-(benzyloxyhexyl)malonate

Product 1

HCID 18920850Diethyl 2,2-bis(6-benzyloxyhexyl)malonateYield 91.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Conditions

Temperature
130 °C

Procedure

First, 1.5 g of 60% sodium hydride and 30 ml of dry dimethylformamide were placed in a 200 ml flask. Then, 30 ml of a dimethylformamide solution containing 11.5 g of diethyl 2-(6-benzyloxyhexyl)malonate was added dropwise to the reaction mixture under ice water cooling, and the resultant reaction mixture was stirred at room temperature for 1 hour and at 130° C. for 30 minutes. Then, 30 ml of a dimethylformamide solution containing 10 g of 1-bromo-6-benzyloxyhexane was added dropwise to the reaction mixture, and the resultant reaction mixture was stirred for 3 hours. The reaction mixture was poured into diluted hydrochloric acid, and an organic layer was extracted with ether. The ether layer was washed with water and dried over anhydrous sodium sulfate. Thereafter, the solvent was distilled away. The residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=9/1) to obtain 14.8 g of diethyl 2,2-bis(6-benzyloxyhexyl)malonate (Y: 91.5%). The compound thus obtained had a purity of 94.7% by GC.

Workup

  1. additionwas added dropwise to the reaction mixture under ice water cooling
  2. customthe resultant reaction mixture
  3. additionwas added dropwise to the reaction mixture
  4. customthe resultant reaction mixture
  5. stirringwas stirred for 3 hours
  6. extractionan organic layer was extracted with ether
  7. washThe ether layer was washed with water
  8. dry with materialdried over anhydrous sodium sulfate
  9. distillationThereafter, the solvent was distilled away
  10. customThe residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=9/1)

Sources & evidence

ORD record
ord-94573a32acbf4417a0628718c4dc7046
Source dataset
uspto-grants-1998_05
Patent number
US05750213

Reaction notes

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