Sulfuric Acid → Ethyl 4,4,4-trifluoro-3-(nitromethyl)butanoate

HRID 530631Notes

Reaction equation

HRID 530631 reaction equation
[F:1][C:2]([F:11])([F:10])/[CH:3]=[CH:4]/[C:5]([O:7][CH2:8][CH3:9])=[O:6].[N+:12]([CH3:15])([O-:14])=[O:13].CN(C)C(=N)N(C)C.S(=O)(=O)(O)O>O>[CH2:8]([O:7][C:5](=[O:6])[CH2:4][CH:3]([CH2:15][N+:12]([O-:14])=[O:13])[C:2]([F:10])([F:11])[F:1])[CH3:9]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 6375NitromethaneHCID 664601,1,3,3-TetramethylguanidineHCID 5371261Ethyl (2E)-4,4,4-trifluoro-2-butenoate

Product 1

HCID 268363Ethyl 4,4,4-trifluoro-3-(nitromethyl)butanoateYield 98%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of 4.203 g (25 mmol) of ethyl 4,4,4-trifluoro-crotonate, 20 mL of nitromethane and ca. 0.576 g (5 mmol) of tetramethyl guanidine was stirred for 13 h at room temperature, and then diluted with water and acidified by the addition of 0.5 M sulfuric acid. The mixture was extracted three times with diethyl ether. The combined ether extracts were washed with water, and then brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. to give 5.601 g (98%) of 4,4,4-trifluoro-3-nitromethyl-butyric acid ethyl ester as an amber oil. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.21 (t, J=7.15 Hz, 3H) 2.76 (dd, J=6.53, 1.76 Hz, 2H) 3.61-3.84 (m, 1H) 4.13 (q, J=7.11 Hz, 2H) 4.83-5.01 (m, 2H).

Workup

  1. extractionThe mixture was extracted three times with diethyl ether
  2. washThe combined ether extracts were washed with water
  3. dry with materialbrine, dried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-20e0dafa53e34ec19e2e5b1d6463eff7
Source dataset
uspto-grants-2016_05
Patent number
US09353096B2

Reaction notes

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