Iodine → Diethyl 2,3-dipropanoylbutanedioate

HRID 851170Notes

Reaction equation

HRID 851170 reaction equation
[O:1]=[C:2]([CH2:9][CH3:10])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[H-].[Na+].II.[OH2:15]>O1CCCC1>[C:2]([CH:3]([CH:3]([C:2](=[O:1])[CH2:9][CH3:10])[C:4]([O:6][CH2:7][CH3:8])=[O:15])[C:4]([O:6][CH2:7][CH3:8])=[O:5])(=[O:1])[CH2:9][CH3:10]

Participants

6

Reactant 4

HCID 807IodineHCID 962WaterHCID 24758Sodium hydrideHCID 78656Ethyl 3-oxovalerate

Product 1

HCID 13126143Diethyl 2,3-dipropanoylbutanedioateYield 91%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Ethyl 3-oxopentanoate (72 g, 0.5 mol) is added dropwise in a nitrogen atmosphere to a suspension of sodium hydride (0.52 mol) in 300 ml of 1:1 anhydrous ether-tetrahydrofuran. After one hour, a solution of iodine (63.5 g, 0.25 mol) in tetrahydrofuran (150 ml) is added and the resulting mixture stirred at ambient temperature for an additional one hour. Water (250 ml) is added and the phases separated. The ether solution is washed with two 50 ml portions of sodium sulfite and dried over sodium sulfate. Removal of the solvent affords 66 g (91%) of diethyl α,β-dipropionylsuccinate. Recrystallization from hexane gives 29 g of solid dimer, mp 80-83 C; IR (CHCl3) 1755, 1730 cm-1 ; NMR (CDCl3) 1.1 (t,6H), 1.3 (t,6H), 2.83 (d of q,4H), 4.18 (q,4H), 4.5 (s,2H).

Workup

  1. customthe phases separated
  2. washThe ether solution is washed with two 50 ml portions of sodium sulfite
  3. dry with materialdried over sodium sulfate
  4. customRemoval of the solvent

Sources & evidence

ORD record
ord-1a2112aaafde40dfb0844f17fb9313cc
Source dataset
uspto-grants-1983_05
Patent number
US04382972

Reaction notes

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