Diethyl Malonate → 1,1-Diethyl cyclopent-3-ene-1,1-dicarboxylate

HRID 2203675Notes

Reaction equation

HRID 2203675 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].Cl[CH2:15]/[CH:16]=[CH:17]\[CH2:18]Cl>O1CCCC1.[Cl-].N>[C:2]1([C:3]([O:5][CH2:6][CH3:7])=[O:4])([C:1]([O:9][CH2:10][CH3:11])=[O:8])[CH2:18][CH:17]=[CH:16][CH2:15]1

Participants

6

Reactant 3

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 64321151,4-Dichloro-cis-2-butene

Product 1

HCID 109875691,1-Diethyl cyclopent-3-ene-1,1-dicarboxylateYield 86%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 20976574Ammonia chlorideSolvent

Procedure

To an ice-cooled solution of diethyl malonate (75.01 g, 468.3 mmol) in tetrahydrofuran (1.5 L) was added sodium hydride (28.1 g, 1.17 mmol) portionwise. After 1 h, (Z)-1,4-dichlorobut-2-ene (75.0 g, 468 mmol) in tetrahydrofuran (500 mL) was added over 40 min at 0° C. After 1 h, the reaction mixture was diluted with saturated aqueous ammonia chloride solution (500 mL), and the resulting mixture was extracted with ethyl acetate (2×2 L). The collected organic was dried over anhydrous sodium sulfate, filtered, and concentrated. Purification by flash column chromatography (petroleum ether) provided product as a yellow oil (85 g, 86% yield).

Workup

  1. waitAfter 1 h
  2. extractionthe resulting mixture was extracted with ethyl acetate (2×2 L)
  3. dry with materialThe collected organic was dried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by flash column chromatography (petroleum ether)

Sources & evidence

ORD record
ord-d029ba85b65840b9a04345d90a632be8
Source dataset
uspto-grants-2016_06
Patent number
US09365583B2

Reaction notes

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