Trimethylsilyl iodide → (Z)-2-bromo-4-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acid

HRID 1502814Notes

Reaction equation

HRID 1502814 reaction equation
[Br:1][C:2]1[CH:12]=[C:11](/[CH:13]=[CH:14]\[CH:15]([C:20]2[CH:25]=[C:24]([Cl:26])[C:23]([Cl:27])=[C:22]([Cl:28])[CH:21]=2)[C:16]([F:19])([F:18])[F:17])[CH:10]=[CH:9][C:3]=1[C:4]([O:6]CC)=[O:5].I[Si](C)(C)C>CC#N>[Br:1][C:2]1[CH:12]=[C:11](/[CH:13]=[CH:14]\[CH:15]([C:20]2[CH:21]=[C:22]([Cl:28])[C:23]([Cl:27])=[C:24]([Cl:26])[CH:25]=2)[C:16]([F:19])([F:18])[F:17])[CH:10]=[CH:9][C:3]=1[C:4]([OH:6])=[O:5]

Participants

4

Reactant 2

HCID 85247Trimethylsilyl iodideHCID 86675135(Z)-ethyl 2-bromo-4-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoate

Product 1

HCID 86675134(Z)-2-bromo-4-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acidYield 42%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a stirred solution of (Z)-ethyl 2-bromo-4-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoate (360 mg, 0.70 mmol) in CH3CN (1.0 mL) was added iodotrimethylsilane (0.28 mL, 2.8 mmol). The reaction mixture was heated to reflux for 20 h, allowed to cool to ambient temperature and partitioned between CH2Cl2 and aq. 10% Na2S2O3. Organic phase was washed once with aq. 10% Na2S2O3 and dried over MgSO4 and concentrated in vacuo. Passing the material through a silica plug with 10% EtOAc in hexanes, followed by 20% MeOH in CH2Cl2) as the eluting solvents afforded the title compound as a yellow foam (143 mg, 42%): mp 54-64° C.; 1H NMR (400 MHz, CDCl3) δ 11.36 (s, 1H), 7.99 (d, J=8.0 Hz, 1H), 7.43 (s, 1H), 7.30 (s, 2H), 7.14 (d, J=7.9 Hz, 1H), 6.85 (d, J=11.4 Hz, 1H), 6.15 (t, J=10.9 Hz, 1H), 4.36-4.09 (m, 1H); 19F NMR (376 MHz, CDCl3) δ −69.30.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 20 h
  3. custompartitioned between CH2Cl2 and aq. 10% Na2S2O3
  4. washOrganic phase was washed once with aq. 10% Na2S2O3
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-674f00da9d024a6487535f81acf4d2a1
Source dataset
uspto-grants-2015_12
Patent number
US09211280B2

Reaction notes

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