Azobisisobutyronitrile → HCID 20728720, compound

HRID 722783Notes

Reaction equation

HRID 722783 reaction equation
[CH:1]([C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([O:17][CH3:18])=[O:16])[CH:10]=2)[C:4]=1[C:19]([O:21][CH3:22])=[O:20])=[CH2:2].[C:23]([OH:26])(=[S:25])[CH3:24].CC(N=NC(C#N)(C)C)(C#N)C>C1C=CC=CC=1>[C:23]([S:25][CH2:2][CH2:1][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([O:17][CH3:18])=[O:16])[CH:10]=2)[C:4]=1[C:19]([O:21][CH3:22])=[O:20])(=[O:26])[CH3:24]

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 20728725HCID 20728725, compoundHCID 178418634HCID 178418634, compound

Product 1

HCID 20728720HCID 20728720, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a solution of 3-ethenyl-[1,1′-biphenyl]-2,3′-dicarboxylic acid, dimethyl ester (0.85 g, 2.9 mmol) in benzene (10 mL) was added thioacetic acid (2.1 mL, 29.4 mmol) followed by AIBN (0.053 g, 0.32 mmol). The solution was deoxygenated for 30 min by bubbling nitrogen through the solution and then heated at reflux for 4 h. Saturated aqueous NaHCO3 (20 mL) was added to the solution and the mixture was extracted with EtOAc (2×20 mL). The combined organic extracts were washed with water and brine, dried over MgSO4, filtered, and concentrated. The residue was purified by flash chromatography (1:12 EtOAc/hexanes) to give 3-[2-(acetylthio)ethyl]-[1,1′-biphenyl]-2,3′-dicarboxylic acid, dimethyl ester (0.51 g, 48%) as an off white solid: 1H NMR (CDCl3) δ 2.35 (s, 3H), 2.93 (m, 2H), 3.14 (m, 2H), 3.62 (s, 3H), 3.93 (s, 3H), 7.29 (dd, J=7.6, 0.9 Hz, 1H), 7.35 (dd, J=7.5, 0.8 Hz, 1H), 7.44 (d, J=7.6 Hz, 1H), 7.48 (d, J=7.5 Hz, 1H), 7.55 (dt, J=8.0, 1.5 Hz, 1H), 8.03 (dt, J=7.9, 1.5 Hz, 1H), 8.07 (t, J=1.5 Hz, 1H).

Workup

  1. customThe solution was deoxygenated for 30 min
  2. customby bubbling nitrogen through the solution
  3. temperatureheated
  4. temperatureat reflux for 4 h
  5. additionSaturated aqueous NaHCO3 (20 mL) was added to the solution
  6. extractionthe mixture was extracted with EtOAc (2×20 mL)
  7. washThe combined organic extracts were washed with water and brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by flash chromatography (1:12 EtOAc/hexanes)

Sources & evidence

ORD record
ord-9b91f78687244065a118000c9418723b
Source dataset
uspto-grants-2006_11
Patent number
US07138543B2

Reaction notes

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