Azobisisobutyronitrile → Dimethyl 4-[2-(acetylthio)ethyl]-1,3-benzenedicarboxylate

HRID 1352812Notes

Reaction equation

HRID 1352812 reaction equation
[CH:1]([C:3]1[CH:8]=[CH:7][C:6]([C:9]([O:11][CH3:12])=[O:10])=[CH:5][C:4]=1[C:13]([O:15][CH3:16])=[O:14])=[CH2:2].CC(N=NC(C#N)(C)C)(C#N)C.[C:29]([OH:32])(=[S:31])[CH3:30]>C1C=CC=CC=1.C([O-])(O)=O.[Na+]>[C:29]([S:31][CH2:2][CH2:1][C:3]1[CH:8]=[CH:7][C:6]([C:9]([O:11][CH3:12])=[O:10])=[CH:5][C:4]=1[C:13]([O:15][CH3:16])=[O:14])(=[O:32])[CH3:30]

Participants

6

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 12017547Dimethyl 4-ethenyl-1,3-benzenedicarboxylateHCID 178418634HCID 178418634, compound

Product 1

HCID 12017548Dimethyl 4-[2-(acetylthio)ethyl]-1,3-benzenedicarboxylateYield 27%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a degassed solution of dimethyl 4-ethenyl-1,3-benzenedicarboxylate (415 mg, 1.88 mmol) in benzene (6 mL) were added AIBN (33 mg, 0.21 mmol) and thioacetic acid (0.27 mL, 3.78 mmol), and the mixture was refluxed for 5 hours. The reaction mixture was diluted with aqueous NaHCO3 solution (15 mL) and extracted with EtOAc (15 mL) The organic layer was dried over MgSO4 and concentrated. The residual material was purified by silica gel chromatography (hexanes/EtOAc=10:1) to give 0.150 9 of colorless oil (27% yield): 1H NMR (CDCl3) δ 2.32 (s, 3H), 3.16 (t, 2H), 3.28 (t, 2H), 3.94 (s, 6H), 7.42 (d, 1H), 8.09 (d, 1H), 8.58 (s, 1H).

Workup

  1. temperaturethe mixture was refluxed for 5 hours
  2. extractionextracted with EtOAc (15 mL) The organic layer
  3. dry with materialwas dried over MgSO4
  4. concentrationconcentrated
  5. customThe residual material was purified by silica gel chromatography (hexanes/EtOAc=10:1)

Sources & evidence

ORD record
ord-76cfa776d09c408d8b366e9aabcb07ab
Source dataset
uspto-grants-2007_05
Patent number
US07220780B2

Reaction notes

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