Azobisisobutyronitrile → HCID 20728722, compound

HRID 722795Notes

Reaction equation

HRID 722795 reaction equation
[CH3:1][O:2][C:3](=[O:17])[C:4]1[C:9]([CH:10]=[CH2:11])=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:12][C:13]([O:15][CH3:16])=[O:14].[C:18]([OH:21])(=[S:20])[CH3:19].CC(N=NC(C#N)(C)C)(C#N)C>C1C=CC=CC=1>[CH3:1][O:2][C:3](=[O:17])[C:4]1[C:5]([CH2:12][C:13]([O:15][CH3:16])=[O:14])=[CH:6][CH:7]=[CH:8][C:9]=1[CH2:10][CH2:11][S:20][C:18](=[O:21])[CH3:19]

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 20728730HCID 20728730, compoundHCID 178418634HCID 178418634, compound

Product 1

HCID 20728722HCID 20728722, compoundYield 33%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Nitrogen was bubbled through a solution of 2-methoxycarbonylmethyl-6-vinyl-benzoic acid methyl ester (1.31 g, 5.60 mmol), thioacetic acid (4.00 mL, 56.0 mmol), and AIBN (0.184 g, 1.10 mmol) in benzene (30 mL) for 3 h at rt to remove oxygen. The mixture was heated at reflux for 3 h. The solution was allowed to cool to rt and saturated aqueous NaHCO3 (100 mL) was added. The mixture was extracted with EtOAc (100 mL) and the organic layer was washed with H2O (100 mL) and brine (100 mL), then dried over MgSO4 and concentrated in vacuo. Flash chromatography on SiO2 (10% EtOAc/hexanes) provided 2-(2-acetylsulfanyl-ethyl)-6-methoxycarbonylmethyl-benzoic acid methyl ester as a yellow solid (0.555 g, 33%): 1H NMR (CDCl3): δ 2.40 (s, 3H), 2.94–2.99 (m, 2H), 3.13–3.18 (m, 2H), 3.75 (s, 3H), 3.78 (s, 2H), 3.99 (s, 3H), 7.25 (d, J=7.6 Hz, 1H), 7.32 (d, J=7.6 Hz, 1H), 7.42 (t, J=7.6 Hz, 1H).

Workup

  1. customto remove oxygen
  2. temperatureThe mixture was heated
  3. temperatureat reflux for 3 h
  4. additionsaturated aqueous NaHCO3 (100 mL) was added
  5. extractionThe mixture was extracted with EtOAc (100 mL)
  6. washthe organic layer was washed with H2O (100 mL) and brine (100 mL)
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-7af83efc4a2a471f91ba9855eac6e896
Source dataset
uspto-grants-2006_11
Patent number
US07138543B2

Reaction notes

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