Hydroxyamine hydrochloride → 4-(3,5-Dimethyl-pyridin-4-yl)-3,5-dimethyl-phenylamine

HRID 1801419Notes

Reaction equation

HRID 1801419 reaction equation
[CH3:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH3:30])[C:7]=1[C:8]1[C:13]([CH3:14])=[CH:12][C:11]([N:15]=C(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:10][C:9]=1[CH3:29].CC([O-])=O.[Na+].Cl.NO>CO>[CH3:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH3:30])[C:7]=1[C:8]1[C:13]([CH3:14])=[CH:12][C:11]([NH2:15])=[CH:10][C:9]=1[CH3:29]

Participants

5

Reactant 3

HCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 595503324-(3,5-dimethylpyridin-4-yl)-N-(diphenylmethylene)-3,5-dimethyl-benzenamine

Product 1

HCID 595503394-(3,5-Dimethyl-pyridin-4-yl)-3,5-dimethyl-phenylamineYield 99%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 9 (0.36 g, 0.93 mmol) in anhydrous MeOH (10 mL) at room temperature was added with stirring NaOAc (0.197 g, 2.40 mmol) and hydroxylamine hydrochloride (0.125 g, 1.80 mmol). The reaction mixture was then stirred at room temperature for 1.5 h. The resulting solution was next partitioned between an aqueous 0.1 M NaOH solution (50 mL) and CH2Cl2 (50 mL×3). The organic layer was separated, dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The crude product was next purified by flash chromatography on silica gel, eluting with ethyl acetate, to give 0.207 g (99.0%) of the title compound as yellow solid: mp 134-135° C.; 1H NMR (400 MHz, CD2Cl2): δ 8.311 (s, 2H), 6.482 (s, 2H), 1.903 (s, 6H), 1.769 (s, 6H); 13C NMR (100 MHz, CD2Cl2): δ 149.130, 148.547, 146.482, 135.882, 132.333, 127.592, 114.635, 19.979, 16.876; MS (ESI): m/z 227.5 [(M+H)+, 100]; Anal. Calcd. for C15H18N2: C, 79.61; H, 8.02; N, 12.38. Found; C, 79.26; H, 7.91; N, 12.04.

Workup

  1. customThe resulting solution was next partitioned between an aqueous 0.1 M NaOH solution (50 mL) and CH2Cl2 (50 mL×3)
  2. customThe organic layer was separated
  3. dry with materialdried over anhydrous Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude product was next purified by flash chromatography on silica gel
  7. washeluting with ethyl acetate

Sources & evidence

ORD record
ord-d5723b480fc848a09c145b37dc69bcbf
Source dataset
uspto-grants-2013_01
Patent number
US08349222B2

Reaction notes

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