Diethyl methylmalonate → HCID 66818335, compound

HRID 1755056Notes

Reaction equation

HRID 1755056 reaction equation
[CH2:1]([O:3][C:4](=[O:12])[CH:5]([CH3:11])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:2].[H-].[Na+].Br[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][O:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>C1COCC1.CCOCC.O>[CH2:1]([O:3][C:4](=[O:12])[C:5]([CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][O:25][CH2:26][C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)([CH3:11])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:2]

Participants

7

Reactant 3

HCID 11857Diethyl methylmalonateHCID 24758Sodium hydrideHCID 11197766HCID 11197766, compound

Product 1

HCID 66818335HCID 66818335, compoundYield 96%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Methyl-malonic acid diethyl ester (0.850 ml, 4.99 mmol) was added to a suspension of sodium hydride (55% oily suspension, 139.5 mg, 3.197 mmol) in THF (0.8 ml) over seven minutes under ice-cooling, and the mixture was stirred until foaming was terminated at room temperature (for about 25 minutes). A solution of (9-bromo-nonyloxymethyl)-benzene (593 mg, 1.89 mmol) in THF (0.12 ml) was added to the reaction solution at room temperature over 15 minutes, and the mixture was then stirred at 90° C. for five hours. The reaction mixture was diluted with ether and water was then added, followed by extraction with ether. The organic layer was dried over MgSO4 and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=30/1→20/1) to give 2-(9-benzyloxy-nonyl)-2-methyl-malonic acid diethyl ester (735 mg, 96%).

Workup

  1. temperaturecooling
  2. customuntil foaming was terminated at room temperature (for about 25 minutes)
  3. stirringthe mixture was then stirred at 90° C. for five hours
  4. additionwas then added
  5. extractionfollowed by extraction with ether
  6. dry with materialThe organic layer was dried over MgSO4
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=30/1→20/1)

Sources & evidence

ORD record
ord-dee833f276d54b549b783e7a0d94182f
Source dataset
uspto-grants-2015_10
Patent number
US09169254B2

Reaction notes

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