Trifluoroacetic acid → HCID 86697934, compound

HRID 1772082Notes

Reaction equation

HRID 1772082 reaction equation
[C:1]([C:5]1[CH:17]=[CH:16][C:8]([C:9]([N:11]([CH2:14][CH3:15])[CH2:12][CH3:13])=[O:10])=[C:7]([CH:18]=O)[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[C:20](=[O:24])([O:22][CH3:23])[NH2:21].FC(F)(F)C(O)=O.C([SiH](CC)CC)C>C(#N)C>[C:1]([C:5]1[CH:17]=[CH:16][C:8]([C:9](=[O:10])[N:11]([CH2:12][CH3:13])[CH2:14][CH3:15])=[C:7]([CH:6]=1)[CH2:18][NH:21][C:20](=[O:24])[O:22][CH3:23])([CH3:2])([CH3:3])[CH3:4]

Participants

6

Reactant 4

HCID 6422Trifluoroacetic acidHCID 11722Methyl CarbamateHCID 12052TriethylsilaneHCID 82544309HCID 82544309, compound

Product 1

HCID 86697934HCID 86697934, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
130 °C

Procedure

A 25-mL microwave vial equipped with a magnetic stirrer was charged with 103a (1.00 g, 3.83 mmol), methyl carbamate (575 mg, 7.66 mmol), trifluoroacetic acid (871 mg, 7.66 mmol), triethylsilane (888 mg, 7.66 mmol) and acetonitrile (10 mL). The vial was loaded in a Biotage microwave and heated at 130° C. for 1.5 h. After this time, the solution was concentrated in vacuo. The resulting residue was partitioned between methylene chloride (100 mL) and a saturated aqueous sodium bicarbonate (30 mL). The aqueous layer was extracted with methylene chloride (3×20 mL). The combined organic layers were washed with brine (30 mL), dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography (silica, 0% to 60% ethyl acetate/hexanes) to afford a 71% yield (858 mg) of 103b as a colorless oil; 1H NMR (300 MHz, CDCl3) δ 7.42 (s, 1H), 7.29 (m, 1H), 7.12 (d, 1H, J=7.7 Hz), 5.60 (br s, 1H), 4.27 (br s, 2H), 3.65 (s, 3H), 3.57 (q, 2H, J=6.8 Hz), 3.20 (q, 2H, J=6.7 Hz), 1.31 (s, 9H), 1.26 (t, 3H, J=6.7 Hz), 1.09 (t, 3H, J=6.8 Hz); MS (ESI+) m/z 321.2 (M+H).

Workup

  1. customA 25-mL microwave vial equipped with a magnetic stirrer
  2. concentrationAfter this time, the solution was concentrated in vacuo
  3. customThe resulting residue was partitioned between methylene chloride (100 mL)
  4. extractionThe aqueous layer was extracted with methylene chloride (3×20 mL)
  5. washThe combined organic layers were washed with brine (30 mL)
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by column chromatography (silica, 0% to 60% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-c3158e6db5ee454a9abd42873fd69117
Source dataset
uspto-grants-2016_02
Patent number
US09249123B2

Reaction notes

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