Trifluoroacetic acid → Carbamate

HRID 588186Notes

Reaction equation

HRID 588186 reaction equation
[N+:1](/[CH:4]=[CH:5]/[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[C:12]([F:15])([F:14])[F:13])([O-:3])=[O:2].C[CH2:17][N:18]([CH2:23][O:24]C)[Si](C)(C)C.F[C:27](F)(F)C(O)=O>C(Cl)Cl>[C:23](=[O:24])([O-:2])[NH2:18].[CH3:17][N:18]1[CH2:23][CH:5]([C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=2[C:12]([F:13])([F:14])[F:15])[CH:4]([N+:1]([O-:3])=[O:2])[CH2:27]1

Participants

6

Reactant 3

HCID 6422Trifluoroacetic acidHCID 5393139TRANS-BETA-NITRO-2-(TRIFLUOROMETHYL)-HCID 87534967HCID 87534967, compound

Product 2

HCID 276CarbamateHCID 118271741HCID 118271741, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

(E)-1-(2-Nitrovinyl)-2-(trifluoromethyl)benzene (230.8 mg, 1.063 mmol) and methyl-methoxymethyltrimethylsilanyl-methylamine (206 mg, 1.275 mmol) was dissolved in DCM (4 mL) and cooled to 0° C. under N2. Trifluoroacetic acid (8.19 μL, 0.106 mmol) was then added and the reaction mixture was stirred at 0° C. for 30 min then warmed to room temperature and stirred for 2 h. The reaction mixture was diluted with DCM and washed with brine. The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo while loading onto silica gel. The residue was purified by flash chromatography (7-60% EtOAc-hexanes) to give (3S and R,4R and S)-1-methyl-3-nitro-4-(2-(trifluoromethyl)phenyl) pyrrolidine. 1H NMR (500 MHz, DMSO-d6) δ 7.84-7.65 (m, 3H), 7.5 (t, J=7.4 Hz, 1H), 5.40-5.34 (m, 1H), 4.18-4.10 (m, 1H), 3.40 (dd, J=3.0, 11.3 Hz, 1H), 3.20 (t, J=8.4 Hz, 1H), 3.10-3.04 (m, 1H), 2.40-2.28 (m, 1H), 2.3 (s, 3H).

Workup

  1. temperaturethen warmed to room temperature
  2. stirringstirred for 2 h
  3. washwashed with brine
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chromatography (7-60% EtOAc-hexanes)

Sources & evidence

ORD record
ord-87b1ace9c11a43b2a79834163ff674d5
Source dataset
uspto-grants-2016_01
Patent number
US09226922B2

Reaction notes

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