Potassium Carbonate → HCID 131729335, compound

HRID 415085Notes

Reaction equation

HRID 415085 reaction equation
Cl[C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:8]=1)[NH2:7].[C:12]([O:16][C:17]([N:19]1[CH2:24][CH2:23][NH:22][CH2:21][CH2:20]1)=[O:18])([CH3:15])(C)C.C(=O)([O-])[O-].[K+].[K+].[CH3:31][C:32](N(C)C)=O>>[NH2:7][C:6]1[CH:8]=[C:2]([N:22]2[CH2:21][CH2:20][N:19]([C:17]([O:16][CH2:12][CH2:15][CH2:31][CH3:32])=[O:18])[CH2:24][CH2:23]2)[CH:3]=[CH:4][C:5]=1[N+:9]([O-:11])=[O:10]

Participants

5

Reactant 4

HCID 11430Potassium CarbonateHCID 31374DimethylacetamideHCID 742185-Chloro-2-nitroanilineHCID 143452tert-Butyl piperazine-1-carboxylate

Product 1

HCID 131729335HCID 131729335, compoundYield 80%

Conditions

Temperature
144 °C

Procedure

5-Chloro-2-nitroaniline (8.60 g, 50 mmol, commercially available from Aldrich), 1-tert-butoxycarbonyl piperazine (14.0 g, 75 mmol, commercially available from Aldrich)), anhydrous potassium carbonate (6.9 g, 50 mmol) and DMA (60 mL) were combined in a thick walled pressure fitted with a Teflon stirrer bar and sealed with a Teflon screw-top stopper. The reaction mixture was heated to 144° C. with stirring for 24 hours. The reaction mixture was allowed to cool to room temperature, filtered and the recovered solid washed with ethyl acetate. The filtrate was partitioned between water and ethyl acetate, and the organic layer was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The resulting crude material was purified by silica chromatography eluting with 25% ethyl acetate-hexane which gave 11.8 g of tent-butyl 4-(3-amino-4-nitrophenyl)piperazine-1-carboxylate (80% yield). 1H-NMR (400 MHz, MeOH-d4): 7.95 (d, 1H), 6.37 (dd, 1H), 6.18 (d, 1H), 3.53 (s, 4H) 3.35 (s, 4H), 1.43 (s, 9H). MS (EI): 323 (MH+).

Workup

  1. customfitted with a Teflon stirrer bar
  2. temperatureto cool to room temperature
  3. filtrationfiltered
  4. washthe recovered solid washed with ethyl acetate
  5. customThe filtrate was partitioned between water and ethyl acetate
  6. washthe organic layer was washed with saturated sodium chloride
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe resulting crude material was purified by silica chromatography
  11. washeluting with 25% ethyl acetate-hexane which

Sources & evidence

ORD record
ord-49aaae5a673e4fd983942f07ad335e48
Source dataset
uspto-grants-2012_01
Patent number
US08088767B2

Reaction notes

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