Diisopropylethylamine → 4-Nitrophenyl 1,1,1-trifluoro-2-methylpropan-2-ylcarbamate

HRID 1629981Notes

Reaction equation

HRID 1629981 reaction equation
[F:1][C:2]([F:8])([F:7])[C:3]([NH2:6])([CH3:5])[CH3:4].Cl[C:10]([O:12][C:13]1[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][CH:14]=1)=[O:11].C(N(C(C)C)CC)(C)C.C(=O)([O-])O.[Na+]>ClCCl>[F:1][C:2]([F:8])([F:7])[C:3]([NH:6][C:10](=[O:11])[O:12][C:13]1[CH:14]=[CH:15][C:16]([N+:19]([O-:21])=[O:20])=[CH:17][CH:18]=1)([CH3:5])[CH3:4]

Participants

6

Reactant 4

HCID 81531DiisopropylethylamineHCID 821294-Nitrophenyl chloroformateHCID 516892Sodium BicarbonateHCID 112751881,1,1-Trifluoro-2-methylpropan-2-amine

Product 1

HCID 665841014-Nitrophenyl 1,1,1-trifluoro-2-methylpropan-2-ylcarbamateYield 26.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-15 °C

Procedure

To a solution of 0.35 g (2.75 mmol) of 1,1,1-trifluoro-2-methylpropan-2-ylamine (CAS 812-18-0) in 20 ml of dichloromethane, cooled to −15° C., is added dropwise 1.00 g (4.96 mmol) of 4-nitrophenyl chloroformate (CAS 7693-46-1) dissolved in 15 ml of dichloromethane, while maintaining the temperature at −15° C. 0.48 ml (2.75 mmol) of diisopropylethylamine in 10 ml of dichloromethane is then added, still at −15° C. Stirring is continued at −15° C. for 2 hours, and the temperature of the mixture is then allowed to return to 0° C. over 1 hour. 20 ml of saturated aqueous sodium hydrogen carbonate solution are then added. The organic phase is separated out by settling and dried over sodium sulfate, and the solvent is partially evaporated off under reduced pressure to a volume of about 8 ml. This solution is chromatographed on a column of 40 g of silica gel, eluting with a mixture of 20% cyclohexane in dichloromethane, to give 0.21 g of 4-nitrophenyl 1,1,1-trifluoro-2-methylpropan-2-ylcarbamate in the form of a white solid.

Workup

  1. waitto return to 0° C. over 1 hour
  2. customThe organic phase is separated out
  3. dry with materialdried over sodium sulfate
  4. customthe solvent is partially evaporated off under reduced pressure to a volume of about 8 ml
  5. customThis solution is chromatographed on a column of 40 g of silica gel
  6. washeluting with a mixture of 20% cyclohexane in dichloromethane

Sources & evidence

ORD record
ord-72ceb5bc7a2249f686eb0c909eb45dc8
Source dataset
uspto-grants-2014_07
Patent number
US08791119B2

Reaction notes

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