Acetic Acid → HCID 59809564, compound

HRID 2114486Notes

Reaction equation

HRID 2114486 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[O:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[Br:17].[C:18]([O:22][C:23]([N:25]1[CH2:30][CH2:29][C:28](=O)[CH2:27][CH2:26]1)=[O:24])([CH3:21])([CH3:20])[CH3:19].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(O)(=O)C>ClC(Cl)C.C(OCC)(=O)C.O>[C:18]([O:22][C:23]([N:25]1[CH2:30][CH2:29][CH:28]([NH:1][C:2]2[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=2[O:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[Br:17])[CH2:27][CH2:26]1)=[O:24])([CH3:21])([CH3:19])[CH3:20]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 5049666Sodium triacetoxyborohydride2×HCID 59809535HCID 59809535, compound2×

Product 1

HCID 59809564HCID 59809564, compoundYield 46%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 63651,1-DichloroethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 4-amino-3-(2-bromophenoxy)-benzonitrile, 2a (0.8 g; 2.77 mmol) and 4-oxo-piperidine-1-carboxylic acid tert-butyl ester (1.1 g; 5.52 mmol) in dichloroethane (80 mL) was added sodium triacetoxyborohydride (1.17 g; 5.52 mmol) and acetic acid (0.16 mL; 2.8 mmol). The mixture was stirred for 2 h at rt. An additional 4 equiv of sodium triacetoxyborohydride was added, and the mixture was heated to 90° C. for 5 h. The mixture was allowed to cool to rt, diluted with ethyl acetate (15 mL) and treated with H2O (15 mL). The organic layer was separated, dried over MgSO4, filtered, and evaporated. The residue was purified via column chromatography (eluent gradient: 0 to 30% ethyl acetate in heptane) to yield 0.6 g (46%) of 4-[2-(2-bromophenoxy)-4-cyanophenylamino]-piperidine-1-carboxylic acid tert-butyl ester, 3a. MS m/z (MH+) 493.7.

Workup

  1. temperaturethe mixture was heated to 90° C. for 5 h
  2. temperatureto cool to rt
  3. customThe organic layer was separated
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customevaporated
  7. customThe residue was purified via column chromatography (eluent gradient: 0 to 30% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-f6cc9bd5ca24430dad9afa2850736cc9
Source dataset
uspto-grants-2008_10
Patent number
US07432257B2

Reaction notes

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