Ethanol → HCID 118349845, compound

HRID 2202729Notes

Reaction equation

HRID 2202729 reaction equation
N#N.[CH2:3]([O:5][C:6]([C@H:8]1[CH2:13][CH2:12][C@H:11]([N:14]2[C:18]([C:19]([F:22])([F:21])[F:20])=[C:17]([C:23]([O:25]CC3C=CC=CC=3)=[O:24])[CH:16]=[N:15]2)[CH2:10][C@H:9]1[CH3:33])=[O:7])[CH3:4].CCO>[Pd].CCOC(C)=O>[CH2:3]([O:5][C:6]([C@H:8]1[CH2:13][CH2:12][C@H:11]([N:14]2[C:18]([C:19]([F:20])([F:21])[F:22])=[C:17]([C:23]([OH:25])=[O:24])[CH:16]=[N:15]2)[CH2:10][C@H:9]1[CH3:33])=[O:7])[CH3:4]

Participants

6

Reactant 3

HCID 702EthanolHCID 947NitrogenHCID 118383363HCID 118383363, compound

Product 1

HCID 118349845HCID 118349845, compoundYield 85.2%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A pressurized vial was charged with palladium 10 wt. % (dry basis) on activated carbon, wet (1.367 g, 1.284 mmol) while under a stream of N2 (gas). Then a solution of benzyl 1-((1S,3R,4S)-4-(ethoxycarbonyl)-3-methylcyclohexyl)-5-(trifluoromethyl)-1H-pyrazole-4-carboxylate (5.631 g, 12.84 mmol) in a 1:1 mixture of EtOH (32.1 ml)/EtOAc (32.1 ml) was added into the vial. The reaction mixture atmosphere was purged with hydrogen gas (3×). The reaction was stirred vigorously under hydrogenation (35 psi) conditions for 2.5 h. The progress of the reaction was monitored by LC/MS, which suggested reaction completion LCMS (ESI) m/z 371.2 (M+Na)+. The mixture was filtered through a plug of celite and the filtrate was concentrated in-vacuo. The residue was diluted with hexane and agitated. The precipitate was collected by filtration and the solids were rinsed with hexane. This gave 1-((1S,3R,4S)-4-(ethoxycarbonyl)-3-methylcyclohexyl)-5-(trifluoromethyl)-1H-pyrazole-4-carboxylic acid (3.810 g, 10.94 mmol, 85% yield) as white solid. 1H NMR (400 MHz, DMSO-d6) δ 7.91-8.21 (m, 1H), 4.47-4.69 (m, 1H), 4.01-4.16 (m, 2H), 2.56-2.70 (m, 1H), 2.12 (dt, J=4.21, 12.37 Hz, 1H), 1.93-2.06 (m, 2H), 1.71-1.90 (m, 3H), 1.19 (t, J=7.04 Hz, 3H), 0.92 (d, J=7.04 Hz, 3H); LCMS (ESI) m/z 371.2 (M+Na)+.

Workup

  1. additionwas added into the vial
  2. customThe reaction mixture atmosphere was purged with hydrogen gas (3×)
  3. customreaction completion LCMS (ESI) m/z 371.2 (M+Na)+
  4. filtrationThe mixture was filtered through a plug of celite
  5. concentrationthe filtrate was concentrated in-vacuo
  6. additionThe residue was diluted with hexane
  7. stirringagitated
  8. filtrationThe precipitate was collected by filtration
  9. washthe solids were rinsed with hexane

Sources & evidence

ORD record
ord-88633b28e6a341689b987b2b921b41c5
Source dataset
uspto-grants-2016_06
Patent number
US09365522B2

Reaction notes

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