Tetrahydrofuran → HCID 12644239, compound

HRID 1744199Notes

Reaction equation

HRID 1744199 reaction equation
C([Mg]Cl)C(C)C.[C:7]([C:14]([O:16][CH2:17][CH3:18])=[O:15])#[C:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].[CH2:19]1[CH2:23]O[CH2:21][CH2:20]1>>[CH2:23](/[C:8](=[CH:7]/[C:14]([O:16][CH2:17][CH3:18])=[O:15])/[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH2:19][CH2:20][CH3:21]

Participants

4

Reactant 3

HCID 8028Tetrahydrofuran3×HCID 69803Diethyl acetylenedicarboxylateHCID 178418368HCID 178418368, compound

Product 1

HCID 12644239HCID 12644239, compoundYield 79%

Conditions

Temperature
-40 °C

Procedure

A mechanically stirred suspension of copper(I) bromide-dimethylsulfide complex (20.4 g, 99.0 mmol) in 500 mL of THF was cooled to −40° C. and treated dropwise with 2.0 M solution of i-butylmagnesium chloride in THF (49.5 mL, 99.0 mmol) under an atmosphere of dry nitrogen. After stirring at −40° C. for 2 h, the reaction mixture was cooled to −78° C. and then treated dropwise with a solution of diethyl acetylenedicarboxylate (13.2 mL, 82.5 mmol) in 160 mL of THF. Upon completion of the addition, the mixture was stirred at −78° C. for 1 h, quenched with saturated NH4Cl aq., then allowed to slowly warm up to room temperature, and stirred at this temperature for additional 30 min. The organic phase was separated and the water phase was thoroughly extracted with ether. The combined organic extracts were washed with saturated NH4Cl aq., then with brine, dried over Na2SO4, and distilled in vacuum to give 14.8 g (79% yield, bp 74–75° C./1 mm Hg) of diethyl 2-1-butylmaleate as a colorless oil.

Workup

  1. temperaturethe reaction mixture was cooled to −78° C.
  2. additionUpon completion of the addition
  3. stirringthe mixture was stirred at −78° C. for 1 h
  4. customquenched with saturated NH4Cl aq.
  5. temperatureto slowly warm up to room temperature
  6. stirringstirred at this temperature for additional 30 min
  7. customThe organic phase was separated
  8. extractionthe water phase was thoroughly extracted with ether
  9. washThe combined organic extracts were washed with saturated NH4Cl aq.
  10. dry with materialwith brine, dried over Na2SO4
  11. distillationdistilled in vacuum

Sources & evidence

ORD record
ord-e72ca070e65e452da132779402639592
Source dataset
uspto-grants-2006_03
Patent number
US07015170B2

Reaction notes

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