Malononitrile → 6-Amino-4-(4-methoxyphenyl)-1-methyl-3-phenyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile

HRID 531204Notes

Reaction equation

HRID 531204 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([CH:9]=O)=[CH:7][CH:8]=1.[C:11](#[N:15])[CH2:12][C:13]#[N:14].C(N(CC)CC)C.[C:23]1([N:29]2[C:33](=[O:34])[CH2:32][C:31]([C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=3)=[N:30]2)C=CC=CC=1>C(O)C>[NH2:14][C:13]1[O:34][C:33]2[N:29]([CH3:23])[N:30]=[C:31]([C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=3)[C:32]=2[CH:9]([C:6]2[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=2)[C:12]=1[C:11]#[N:15]

Participants

6

Reactant 4

HCID 8010MalononitrileHCID 8471TriethylamineHCID 312444-MethoxybenzaldehydeHCID 785593H-Pyrazol-3-one, 2,4-dihydro-2,5-diphenyl-

Product 1

HCID 896467086-Amino-4-(4-methoxyphenyl)-1-methyl-3-phenyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrileYield 87.1%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of anisaldehyde (350 μL, 2.87 mmol, 1.0 equ.), malononitrile (190 mg, 2.87 mmol, 1.0 equ.) and triethylamine (400 μL, 2.87 mmol, 1.0 equ.) in ethanol (10 mL) is stirred for 1 min, followed by the addition of 1,3-diphenyl-1H-pyrazol-5(4H)-one (678 mg, 2.87 mmol, 1 equ.). The reaction mixture was concentrated after 24 h and the precipitate was washed with ethanol and hexanes. The product was re-crystallized from ethanol to afford 6-amino-4-(4-methoxyphenyl)-1-methyl-3-phenyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (1.05 g, 87%, 2.50 mmol) as a white solid. 1H-NMR (400 MHz) DMSO: 7.94-7.92 (d, 2H), 7.63-7.61 (d, 2H), 7.57-7.53 (t, 2H), 7.40-7.36 (t, 1H), 7.29-7.23 (m, 3H) 7.15 (s, 2H), 7.13-7.11 (d, 2H), 6.78-6.76 (d, 2H), 5.02 (s, 1H), 3.65 (s, 3H), 13C-NMR (100 MHz) DMSO: 158.9, 158.4, 146.7, 145.6, 137.9, 136.5, 132.6, 129.8, 129.0, 128.7, 128.5, 127.2, 127.0, 121.2, 120.3, 114.2, 98.3, 60.2, 55.3, 37.1; LC/MS-MS: 421.2→355.0 m/z; GS1 and GS2 at 30, DP=81, CE=35, CXP=24, tR=4.32 min.

Workup

  1. concentrationThe reaction mixture was concentrated after 24 h
  2. washthe precipitate was washed with ethanol and hexanes
  3. customThe product was re-crystallized from ethanol

Sources & evidence

ORD record
ord-26e81170a1484c7287db7841b781ab41
Source dataset
uspto-grants-2016_05
Patent number
US09353121B2

Reaction notes

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