Toluene → methyl (Z)-2-(2-oxotetrahydro-1H-1-pyrrolyl)-2-butenoate

HRID 1351754Notes

Reaction equation

HRID 1351754 reaction equation
O=[C:2]([CH2:7][CH3:8])[C:3]([O:5][CH3:6])=[O:4].C1(C)C=CC=CC=1.[NH:16]1[CH2:20][CH2:19][CH2:18][C:17]1=[O:21].O=P(Cl)(Cl)Cl>O>[O:21]=[C:17]1[CH2:18][CH2:19][CH2:20][N:16]1/[C:2](=[CH:7]\[CH3:8])/[C:3]([O:5][CH3:6])=[O:4]

Participants

6

Reactant 4

HCID 1140TolueneHCID 120252-PyrrolidoneHCID 24813Phosphorus oxychlorideHCID 5451272-Ketobutyric acid methyl ester

Product 1

HCID 59076257methyl (Z)-2-(2-oxotetrahydro-1H-1-pyrrolyl)-2-butenoateYield 60%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A 100 ml flask fitted with a magnetic stirring bar and a Dean-Stark trap was charged with methyl 2-oxobutanoate (7.5 g, 73 mmol), toluene (50 ml, 7 vol) and 2-pyrrolidinone (8.4 ml, 111 mmol, 1.5 equiv) followed by dropwise addition of POCl3 (1.6 ml, 20 mmol, 0.27 equiv). The reaction mixture was stirred under reflux with azeotropic removal of water via the Dean-Stark trap for 8 hours. After cooling down the solution was washed with 10% aq KHSO4 (2×3 vol). The aqueous phase was saturated with NaCl and back extracted with toluene (1×6 vol). The combined organic phase was dried over MgSO4, filtered and concentrated in vacuo to afford crude material (7.5 g) as an orange mobile oil. The crude oil was distilled (92–94° C., 0.1 mm Hg) and gave pure product (4.7 g, 60%) as a colourless oil.

Workup

  1. customA 100 ml flask fitted with a magnetic stirring bar
  2. temperatureAfter cooling down the solution
  3. washwas washed with 10% aq KHSO4 (2×3 vol)
  4. extractionback extracted with toluene (1×6 vol)
  5. dry with materialThe combined organic phase was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto afford crude material (7.5 g) as an orange mobile oil
  9. distillationThe crude oil was distilled (92–94° C., 0.1 mm Hg)

Sources & evidence

ORD record
ord-2026996b634f4735abfa332aa85bfca1
Source dataset
uspto-grants-2007_05
Patent number
US07217826B2

Reaction notes

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