Methanol → 2,6-Diisopropyl-N-{[6-(2-{[(2-methylphenyl)amino]methyl}-1-naphthyl)pyridin-2-yl]methyl}aniline

HRID 1944827Notes

Reaction equation

HRID 1944827 reaction equation
[CH:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([CH:10]([CH3:12])[CH3:11])[C:5]=1[N:13]=[CH:14][C:15]1[CH:20]=[CH:19][CH:18]=[C:17]([C:21]2[C:30]3[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=3)[CH:24]=[CH:23][C:22]=2[CH2:31][NH:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][C:34]=2[CH3:39])[N:16]=1)([CH3:3])[CH3:2].CO.[BH3-]C#N.[Na+]>C(O)=O.O>[CH:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([CH:10]([CH3:12])[CH3:11])[C:5]=1[NH:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[C:17]([C:21]2[C:30]3[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=3)[CH:24]=[CH:23][C:22]=2[CH2:31][NH:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][C:34]=2[CH3:39])[N:16]=1)([CH3:2])[CH3:3]

Participants

6

Reactant 3

HCID 887MethanolHCID 5003444Sodium cyanoborohydrideHCID 66799583(2,6-Diisopropylphenyl){[6-(2-{[(2-methylphenyl)amino]methyl}-1-naphthyl)pyridin-2-yl]methylene}amine

Product 1

HCID 667960522,6-Diisopropyl-N-{[6-(2-{[(2-methylphenyl)amino]methyl}-1-naphthyl)pyridin-2-yl]methyl}aniline

Reagents, catalysts & solvents 2

HCID 284Formic AcidCatalystHCID 962WaterSolvent

Procedure

To a solution of 1.50 g (2.90 mmol) of (2,6-diisopropylphenyl){[6-(2-{[(2-methylphenyl)amino]methyl}-1-naphthyl)pyridin-2-yl]methylene}amine in 20 ml of methanol 0.30 g (4.70 mmol) of NaBH3CN was added in one portion followed by addition of three drops of 88% formic acid. The reaction mixture was refluxed for 1 h and then poured into 50 ml of water. The crude product was extracted with 2×20 ml of ether. The organic extract was washed by water, dried over K2CO3, and then evaporated to dryness. The product was isolated by flash chromatography on silica gel 60 (40-63 um; eluent: hexanes-ethyl acetate=5:1, vol.). Yield 1.00 g (67%) of yellow oil which crystallized at room temperature. Anal. calc. for C36H39N3: C, 84.17; H, 7.65; N, 8.18. Found: C, 84.25; H, 7.78; N, 8.00. 1H NMR (CDCl3): 7.91 (d, J=8.4 Hz, 1H, 4-H in naphthyl), 7.89 (m, 1H, 8-H in naphthyl), 7.79 (m, 1H, 4-H in Py), 7.66 (d, J=8.4 Hz, 1H, 3-H in naphthyl), 7.47 (m, 1H, 7-H in naphthyl), 7.36-7.42 (m, 4H, 3,5-H in Py and 5,6-H in naphthyl), 7.04-7.10 (m, 3H, 3,5-H in ortho-tolyl and 4-H in 2,6-diisopropylphenyl), 7.01 (m, 2H, 3,5-H in 2,6-diisopropylphenyl), 6.61 (m, 1H, 4-H in ortho-tolyl), 6.52 (m, 1H, 6-H in ortho-tolyl), 4.22-4.35 (m, 4H, CH2N), 4.02 (br. s, 1H, NH), 3.93 (br. s, 1H, NH), 3.28 (sept, J=6.8 Hz, 2H, CHMe2), 2.09 (s, 3H, Me in ortho-tolyl), 1.16 (d, J=6.8 Hz, 6H, CHMeMe′), 1.14 (d, J=6.8 Hz, 6H, CHMeMe′).

Workup

  1. temperatureThe reaction mixture was refluxed for 1 h
  2. extractionThe crude product was extracted with 2×20 ml of ether
  3. extractionThe organic extract
  4. washwas washed by water
  5. dry with materialdried over K2CO3
  6. customevaporated to dryness
  7. customThe product was isolated by flash chromatography on silica gel 60 (40-63 um; eluent: hexanes-ethyl acetate=5:1, vol.)
  8. customYield 1.00 g (67%) of yellow oil which crystallized at room temperature

Sources & evidence

ORD record
ord-f347a0bf6e5441d0a8599a876eb7adc4
Source dataset
uspto-grants-2013_03
Patent number
US08394902B2

Reaction notes

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