Tributylvinyltin → 2-Amino-4-trifluoromethyl-5-vinyl-benzoic acid methyl ester

HRID 507048Notes

Reaction equation

HRID 507048 reaction equation
[NH2:1][C:2]1[CH:11]=[C:10]([C:12]([F:15])([F:14])[F:13])[C:9](I)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[CH2:17]([Sn](CCCC)(CCCC)C=C)[CH2:18]CC>C1(C)C=CC=CC=1.C(OCC)(=O)C>[CH3:7][O:6][C:4](=[O:5])[C:3]1[CH:8]=[C:9]([CH:17]=[CH2:18])[C:10]([C:12]([F:15])([F:14])[F:13])=[CH:11][C:2]=1[NH2:1]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 53436880Methyl 2-amino-5-iodo-4-(trifluoromethyl)benzoate

Product 1

HCID 594324892-Amino-4-trifluoromethyl-5-vinyl-benzoic acid methyl esterYield 71.2%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Add tetrakis palladium(triphenylphosphine)(0) (5.00 g, 4.33 mmol) to a mixture of 2-amino-5-iodo-4-trifluoromethyl-benzoic acid methyl ester (Example 3, Step 3) (17.25 g, 49.99 mmol) and tributyl(vinyl)tin (16.10 mL, 55.14 mmol) in toluene (500 mL) and heat at reflux for 14 h. Allow the reaction to cool to room temperature dilute the mixture with ethyl acetate (1 L). Wash the mixture with saturated aqueous potassium fluoride solution (3×300 mL), then water (300 mL), followed by brine (500 mL). Dry the organic layer over anhydrous sodium sulfate, filter, and remove the solvents under reduced pressure. Purify the residue by column chromatography on silica gel, eluting with ethyl acetate/hexanes (0 to 15%), to provide the title compound as a pale yellow solid (8.73 g, 71%): TLC Rf 0.52 (3:1 hexanes/ethyl acetate); 1H NMR (CDCl3, 300 MHz) δ 3.89 (s, 3H), 5.21-5.30 (m, 1H), 5.60-5.71 (m, 1H), 5.98 (bs, 2H), 6.83-7.02 (m, 2H), 8.19 (s, 1H).

Workup

  1. temperatureheat
  2. temperatureat reflux for 14 h
  3. customthe reaction
  4. washWash the mixture with saturated aqueous potassium fluoride solution (3×300 mL)
  5. dry with materialDry the organic layer over anhydrous sodium sulfate
  6. filtrationfilter
  7. customremove the solvents under reduced pressure
  8. customPurify the residue by column chromatography on silica gel
  9. washeluting with ethyl acetate/hexanes (0 to 15%)

Sources & evidence

ORD record
ord-8e965c236ce949aa921e75e05d2b380c
Source dataset
uspto-grants-2010_08
Patent number
US07786108B2

Reaction notes

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