Diisopropylethylamine → 4-Nitrophenyl 4,4,4-trifluorobutylcarbamate

HRID 1629975Notes

Reaction equation

HRID 1629975 reaction equation
[F:1][C:2]([F:8])([F:7])[CH2:3][CH2:4][CH2:5][NH2:6].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])[CH2:3][CH2:4][CH2:5][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

Participants

6

Reactant 4

HCID 81531DiisopropylethylamineHCID 821294-Nitrophenyl chloroformateHCID 1366454,4,4-TrifluorobutylamineHCID 516892Sodium Bicarbonate

Product 1

HCID 665841404-Nitrophenyl 4,4,4-trifluorobutylcarbamateYield 94.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-15 °C

Procedure

To a solution of 0.35 g (2.75 mmol) of 4,4,4-trifluoro-butylamine (CAS 819-46-5) 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 still at −15° C. is then added. Stirring is continued at −15° C. for 45 minutes, and the temperature of the mixture is then allowed to return to 0° C. over 30 minutes. 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 0.76 g of 4-nitrophenyl 4,4,4-trifluorobutylcarbamate in the form of a white solid.

Workup

  1. waitto return to 0° C. over 30 minutes
  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-0346689324cb42a1b0581b8878f50f9d
Source dataset
uspto-grants-2014_07
Patent number
US08791119B2

Reaction notes

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