Hydrochloric Acid → HCID 2807828, compound

HRID 2425556Notes

Reaction equation

HRID 2425556 reaction equation
[Li+].[BH4-].[CH3:3][N:4]1[C:8]([C:9]([F:12])([F:11])[F:10])=[C:7]([C:13](OCC)=[O:14])[CH:6]=[N:5]1.Cl.C(=O)([O-])[O-].[Na+].[Na+].C1C([N+]([O-])=O)=CC([N+]([O-])=O)=C(NN)C=1>C1COCC1.ClCCl.C(Cl)Cl.C(OCC)(=O)C.O>[CH3:3][N:4]1[C:8]([C:9]([F:10])([F:11])[F:12])=[C:7]([CH2:13][OH:14])[CH:6]=[N:5]1

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 2737211ethyl 1-methyl-5-(trifluoromethyl)-1H-pyrazole-4-carboxylateHCID 3772977(2,4-Dinitrophenyl)hydrazineHCID 4148881Lithium borohydride

Product 1

HCID 2807828HCID 2807828, compound

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×HCID 21226138Dichloromethane ethylacetateSolvent

Procedure

LiBH4 in THF (2M, 15 ml, 0.03 mole) was added dropwise to a stirred solution of ethyl 1-methyl-5-(trifluoromethyl)-1H-pyrazole-4-carboxylate (3.32 g, 0.015 mole) in THF (40 ml) at room temperature under nitrogen. The solution was then stirred under reflux for 18 hrs. After cooling, the cloudy solution was evaporated at room temperature to give an oil. Water was added (heavy ppt. of white solid) and the mixture chilled and treated cautiously with hydrochloric acid (2M) to pH 2 (no solid remaining, to give an oil). The mixture was neutralised with sodium carbonate and the mixture extracted with diethyl ether (3×20 ml). The organic layer was separated and back-washed with brine (3×30 ml). The organic layer was separated, dried (Na2SO4), filtered and evaporated to give an oil. Yield 3 g. An aliquot (150 mg) was dissolved in dichloromethane and purified using an ISCO Companion (4 g silica col. CH2Cl2 to CH2Cl2:ethyl acetate 9:1). The appropriate fractions were combined and evaporated to give an oil, 72 mg. 1H NMR (400 MHz, CDCl3) δ 7.54 (s, 1H) 4.69, 4.48 (d, 2H) 4.00 (s, 3H) 1.70, 1.68, 1.67 (t, 1H). MS (ESI) m/z 181 (M+H)+. LC-MS m/z 181 (M+H) GC-MS FID 100% Cl+ 181 (M+H)+. TLC CH2Cl2:ethyl acetate 9:1 0.25 UV−ve DNPH+ve.

Workup

  1. temperatureunder reflux for 18 hrs
  2. temperatureAfter cooling
  3. customthe cloudy solution was evaporated at room temperature
  4. customto give an oil
  5. temperaturethe mixture chilled
  6. customto give an oil)
  7. extractionthe mixture extracted with diethyl ether (3×20 ml)
  8. customThe organic layer was separated
  9. washback-washed with brine (3×30 ml)
  10. customThe organic layer was separated
  11. dry with materialdried (Na2SO4)
  12. filtrationfiltered
  13. customevaporated
  14. customto give an oil
  15. custompurified
  16. customevaporated
  17. customto give an oil, 72 mg

Sources & evidence

ORD record
ord-faedc91b9d9d4461b4fd6c9854fb896c
Source dataset
uspto-grants-2011_06
Patent number
US07964732B2

Reaction notes

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