Acetic Acid → HCID 13336314, compound

HRID 1668471Notes

Reaction equation

HRID 1668471 reaction equation
[Br:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[CH3:9][N:10]1[CH2:15][CH2:14][C:13](=O)[CH2:12][CH2:11]1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[OH-].[Na+]>ClC(Cl)C>[NH3:6].[Br:1][C:2]1[CH:8]=[CH:7][C:5]([NH:6][CH:13]2[CH2:14][CH2:15][N:10]([CH3:9])[CH2:11][CH2:12]2)=[CH:4][CH:3]=1

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 78074-BromoanilineHCID 14798Sodium HydroxideHCID 740491-Methyl-4-piperidoneHCID 5049666Sodium triacetoxyborohydride

Product 2

HCID 222AmmoniaHCID 13336314HCID 13336314, compoundYield 127.8%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

4-bromoaniline (1.0 g, 5.813 mmol) was dissolved in anhydrous dichloroethane (30 mL) in a dry argon purged flask fitted with a magnetic stir bar. 1-methylpiperidin-4-one (671 ul, 5.813 mmol), acetic acid (329 ul, 5.813 mmol) and sodium triacetoxyborohydride (1.848 g, 8.719 mmol) are added to the flask and mixture stirred at ambient temperature for 22 hours then heated to 55° C. for 4 hours. After cooling to room temperature, the mixture was transferred to a separatory funnel and 1M sodium hydroxide solution added to adjust pH to 10. The organic layer was collected and the aqueous layer further extracted with dichloromethane. The combined organic layers were washed with brine, dried over magnesium sulphate, filtered, concentrated and the crude purified via chromatography on silica gel (methanol:CH2Cl2, 5:95 then 2M NH3 in methanol:CH2Cl2, 1:9) to yield an off-white solid, 78 (1.0 g, 63.9%). 1H NMR (CDCl3) δ 1.40-1.58 (m, 2H), 1.98-2.22 (m, 4H), 2.31 (s, 3H), 2.73-2.89 (m, 2H), 3.15-3.32 (m, 1H), 3.45-3.58 (m, 1H), 6.47 (d, 2H, J=8.8 Hz), 7.23 (d, 2H, J=8.8 Hz); ESI-MS (m/z, %): 269/271 (MH+, 100%).

Workup

  1. customfitted with a magnetic stir bar
  2. temperaturethen heated to 55° C. for 4 hours
  3. temperatureAfter cooling to room temperature
  4. customthe mixture was transferred to a separatory funnel
  5. customThe organic layer was collected
  6. extractionthe aqueous layer further extracted with dichloromethane
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over magnesium sulphate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customthe crude purified via chromatography on silica gel (methanol

Sources & evidence

ORD record
ord-b4d4e3ced534402abbca02581c3c2bd2
Source dataset
uspto-grants-2011_08
Patent number
US07989447B2

Reaction notes

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