Sodium Chloride → Triethyl ethane-1,1,2-tricarboxylate

HRID 2058146Notes

Reaction equation

HRID 2058146 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([O-:5])=[O:4].Br[CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13].[Cl-].[Na+].Cl[CH:20](Cl)[CH3:21]>O1CCCC1>[CH2:8]([O:7][C:1](=[O:6])[CH:2]([C:3]([O:5][CH2:20][CH3:21])=[O:4])[CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH3:9]

Participants

6

Reactant 4

HCID 5234Sodium ChlorideHCID 63651,1-DichloroethaneHCID 7748Ethyl bromoacetateHCID 3595298Propanedioic acid, monoethyl ester

Product 1

HCID 81961Triethyl ethane-1,1,2-tricarboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Diethyl-2-carbethoxysuccinate (formula 3, in which R are ethyl groups) is prepared by dissolving ethyl malonate (66 g, 0.5 moles) in tetrahydrofuran (500 ml). Sodium hydride (19.7 g of a 66% suspension in oil) (0.5 mole) is washed twice with petroleum ether (b.p. 30°-66°) and added to the stirred solution in small portions. Ethyl bromoacetate (83.5 g, 0.5 moles) is then added slowly from a dropping funnel. After stirring for 16 hours, the resultant white suspension is transferred to a separatory funnel along with a saturated aqueous sodium chloride solution (1 liter) and dichloroethane (1 liter). After shaking and separating the layers, the water layer is extracted with two additional liter portions of dichloroethane. The combined organic layers are dried over sodium sulfate before filtration and evaporation. The crude product is distilled under reduced pressure and the fractions boiling at 105°-112° at 2.5 mm Hg (12 ml) and 112°-115° (25 ml) are kept for use in the reaction of the next example.

Workup

  1. washSodium hydride (19.7 g of a 66% suspension in oil) (0.5 mole) is washed twice with petroleum ether (b.p. 30°-66°)
  2. additionadded to the stirred solution in small portions
  3. stirringAfter shaking
  4. customseparating the layers
  5. extractionthe water layer is extracted with two additional liter portions of dichloroethane
  6. dry with materialThe combined organic layers are dried over sodium sulfate before filtration and evaporation
  7. distillationThe crude product is distilled under reduced pressure
  8. customat 2.5 mm Hg (12 ml) and 112°-115° (25 ml)

Sources & evidence

ORD record
ord-5e702860252f4f9c808facb4764ce7d1
Source dataset
uspto-grants-1980_07
Patent number
US04215062

Reaction notes

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