Acetic Acid → Ammonia

HRID 843165Notes

Reaction equation

HRID 843165 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[O:7][C:8]2[CH:15]=[CH:14][CH:13]=[C:12]([O:16][CH:17]3[CH2:22][CH2:21][NH:20][CH2:19][CH2:18]3)[C:9]=2[C:10]=1[CH3:11])=[O:5])[CH3:2].[N:23]1[CH:28]=[CH:27][CH:26]=[C:25]([CH:29]=O)[CH:24]=1.C(O)(=O)C.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C1COCC1.C(OCC)(=O)C>[NH3:20].[CH2:1]([O:3][C:4]([C:6]1[O:7][C:8]2[CH:15]=[CH:14][CH:13]=[C:12]([O:16][CH:17]3[CH2:18][CH2:19][N:20]([CH2:29][C:25]4[CH:24]=[N:23][CH:28]=[CH:27][CH:26]=4)[CH2:21][CH2:22]3)[C:9]=2[C:10]=1[CH3:11])=[O:5])[CH3:2]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 103713-PyridinecarboxaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 53778444HCID 53778444, compound

Product 2

HCID 222AmmoniaYield 25%HCID 53974102HCID 53974102, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-Methyl-4-(piperidin-4-yloxy)-benzofuran-2-carboxylic acid ethyl ester (44 mg), pyridine-3-aldehyde (41 μl) and acetic acid (50 μl) were dissolved in THF (2 ml). The solution was stirred at room temperature for one hour. To a solution was added NaB(OAc)3H (160 mg) and the resulting suspension was stirred at room temperature for two hours. The reaction mixture was diluted with ethyl acetate and washed with saturated sodium hydrogencarbonate solution and water. The organic solvent was dried over anhydrous sodium sulfate and evaporated to dryness. The residue was purified by preparative thin layer chromatography (using dichloromethane:MeOH:ammonia solution (25-28%)=10:1:0.2 as a developing solvent) to give 3-methyl-4-(1-pyridin-3-ylmethyl-piperidin-4-yloxy)-benzofuran-2-carboxylic acid ethyl ester (44 mg) as a colorless oil. MALDI-TOF-MS: m/z 395 (MH+); 1H-NMR (CDCl3): δ 1.44 (3H, t, J=7 Hz), 2.02 (4H, m), 2.47 (2H, m), 2.72 (2H, m), 2.75 (3H, s). 3.56 (2H, s), 4.44 (2H, q, J=7 Hz), 4.58 (1H, m), 6.62 (1H, d, J=8 Hz), 7.09 (1H, d, J=8 Hz), 7.28 (1H, t, J=8 Hz), 7.29 (1H, m), 7.71 (1H, brd, J=8 Hz), 8.53 (1H, brd, J=4 Hz), 8.56 (1H, br s).

Workup

  1. stirringthe resulting suspension was stirred at room temperature for two hours
  2. washwashed with saturated sodium hydrogencarbonate solution and water
  3. dry with materialThe organic solvent was dried over anhydrous sodium sulfate
  4. customevaporated to dryness
  5. customThe residue was purified by preparative thin layer chromatography (

Sources & evidence

ORD record
ord-f48100ec6bb84a70863829e528ab69d4
Source dataset
uspto-grants-2002_04
Patent number
US06376491B1

Reaction notes

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