Acetic Anhydride → HCID 69036363, compound

HRID 1930481Notes

Reaction equation

HRID 1930481 reaction equation
[C:1]([C:5]1[CH:9]=[C:8]([NH:10][C:11](=[O:18])[O:12][CH2:13][C:14]([Cl:17])([Cl:16])[Cl:15])[N:7]([C:19]2[CH:24]=[CH:23][CH:22]=[C:21]([N+:25]([O-])=O)[CH:20]=2)[N:6]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:28][C:29](OC(C)=O)=[O:30]>CCOC(C)=O.[Pd]>[C:29]([NH:25][C:21]1[CH:20]=[C:19]([N:7]2[C:8]([NH:10][C:11](=[O:18])[O:12][CH2:13][C:14]([Cl:17])([Cl:16])[Cl:15])=[CH:9][C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])=[N:6]2)[CH:24]=[CH:23][CH:22]=1)(=[O:30])[CH3:28]

Participants

5

Reactant 2

HCID 7918Acetic AnhydrideHCID 69037844HCID 69037844, compound

Product 1

HCID 69036363HCID 69036363, compoundYield 73%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

2,2,2-Trichloroethyl 3-t-butyl-1-(3-nitrophenyl)-1H-pyrazol-5-ylcarbamate (0.67 g, 1.538 mmol, 1.00 eq) in EtOAc (30 ml) was shaken under H2 (3.5 arm) at 22° C. over 10% Pd/C (0.327 g, 0.154 mmol, 0.10 eq, 50% H2O) overnight. The completed hydrogenation was treated with Ac2O (3 ml) and stirred at RT. After 45 min, the mixture was filtered through Celite, rinsing forward with EtOAc. The filtrate was treated with a roughly equal volume of satd. NaHCO3 and stirred briskly at RT for 3 h. The layers were separated and the organic layer washed with satd. NaHCO3 (2×). The combined aqueous layers were extracted with EtOAc (1×). The combined organics were washed with brine (1×), dried (MgSO4), filtered and evaporated to afford 2,2,2-trichloroethyl 1-(3-acetamidophenyl)-3-t-butyl-1H-pyrazol-5-ylcarbamate (0.50 g, 73% yield) as a white solid which was used as is in the next reaction. 1H NMR (400 MHz, DMSO-d6): δ 10.10 (s, 1H), 9.95 (brs, 1H), 7.74 (brs, 1H), 7.54-7.51 (m, 1H), 7.37-7.31 (m, 1H), 7.08 (d, J=7.6 Hz, 1H), 6.26 (s, 1H), 4.84 (s, 2H), 2.03 (s, 3H), 1.26 (s, 9H); MS (ESI) m/z: 447.0 (M+H), 449.0 ((M+2+H).

Workup

  1. filtrationthe mixture was filtered through Celite
  2. washrinsing forward with EtOAc
  3. additionThe filtrate was treated with a roughly equal volume of satd
  4. stirringNaHCO3 and stirred briskly at RT for 3 h
  5. customThe layers were separated
  6. washthe organic layer washed with satd
  7. extractionThe combined aqueous layers were extracted with EtOAc (1×)
  8. washThe combined organics were washed with brine (1×)
  9. dry with materialdried (MgSO4)
  10. filtrationfiltered
  11. customevaporated

Sources & evidence

ORD record
ord-7f4a70cf39ae46fcb41a3a43fb893e75
Source dataset
uspto-grants-2012_05
Patent number
US08188113B2

Reaction notes

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