Acrylonitrile → 4,5-Dihydro-1-(3-(trifluoromethyl)phenyl)-1H-pyrazol-3-amine

HRID 1455613Notes

Reaction equation

HRID 1455613 reaction equation
[O-]CC.[Na+].[F:5][C:6]([F:16])([F:15])[C:7]1[CH:8]=[C:9]([NH:13][NH2:14])[CH:10]=[CH:11][CH:12]=1.[C:17](#[N:20])[CH:18]=[CH2:19]>C(O)C>[F:5][C:6]([F:15])([F:16])[C:7]1[CH:8]=[C:9]([N:13]2[CH2:19][CH2:18][C:17]([NH2:20])=[N:14]2)[CH:10]=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 7855AcrylonitrileHCID 98650(3-(Trifluoromethyl)phenyl)hydrazineHCID 2723922Sodium ethoxide

Product 1

HCID 477954,5-Dihydro-1-(3-(trifluoromethyl)phenyl)-1H-pyrazol-3-amine

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Sodium ethoxide (3.9 g, 0.056 mmol) dissolved in ethanol (100 mL) and 3-(trifluoromethyl) phenylhydrazine (5 g, 0.028 mol) added followed by acrylonitrile (2.3 mL, 0.035 mol) and heated to reflux for 24 h. The solution was then evaporated to dryness in vacuo and water added. The solution was then extracted into dichloromethane and the organics combined, dried (Na2SO4), filtered and evaporated to dryness. The residue was then passed through a silica gel column eluting with dichloromethane:methanol. Product fractions collected and evaporated to dryness, dissolved in dichloromethane and 1M hydrogen chloride in diethyl ether added to form a white solid which was collected by filtration and dried (3 g, 40%). 1H NMR (400 MHz, CD3OD) δ ppm 3.23 (2H, br m), 4.04 (2H, br m), 7.32-7.37 (3H, br m), 7.56 (1H, br s). MS (ES) m/z: 230.0 [M+H].

Workup

  1. temperatureheated
  2. temperatureto reflux for 24 h
  3. customThe solution was then evaporated to dryness in vacuo and water
  4. additionadded
  5. extractionThe solution was then extracted into dichloromethane
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated to dryness
  9. washeluting with dichloromethane
  10. customProduct fractions collected
  11. customevaporated to dryness
  12. dissolutiondissolved in dichloromethane
  13. addition1M hydrogen chloride in diethyl ether added
  14. customto form a white solid which
  15. filtrationwas collected by filtration
  16. customdried (3 g, 40%)

Sources & evidence

ORD record
ord-b79a98cb06044a519f500081c372beb4
Source dataset
uspto-grants-2009_01
Patent number
US07482469B2

Reaction notes

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