Malononitrile → HCID 89646849, compound

HRID 531206Notes

Reaction equation

HRID 531206 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.[CH3:23][O:24][C:25]1[CH:30]=[CH:29][C:28]([C:31]2[CH2:35][C:34](=[O:36])[N:33]([CH3:37])[N:32]=2)=[CH:27][CH:26]=1>C(O)C>[NH2:14][C:13]1[O:36][C:34]2[N:33]([CH3:37])[N:32]=[C:31]([C:28]3[CH:27]=[CH:26][C:25]([O:24][CH3:23])=[CH:30][CH:29]=3)[C:35]=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 15145018HCID 15145018, compound

Product 1

HCID 89646849HCID 89646849, compoundYield 62%

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) was stirred for 1 min, followed by the addition of 3-(4-methoxyphenyl)-1-methyl-1H-pyrazol-5(4H)-one (689 mg, 2.87 mmol, 1 equiv.). The reaction mixture was concentrated after 24 h and the precipitate was washed with ethanol and hexanes, and then re-crystallized from ethanol to give 6-amino-3,4-bis(4-methoxyphenyl)-1-methyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (690 mg, 1.78 mmol, 62%) as a white solid. 1H-NMR (400 MHz) DMSO: 7.42-7.40 (d, 2H), 7.05-7.03 (d, 2H), 7.00 (s, 2H), 6.78-6.75 (dd, 4H), 4.86 (s, 1H), 3.73 (s, 3H), 3.68 (s, 3H), 3.66 (s, 3H), 13C-NMR (100 MHz) DMSO: 159.0, 158.9, 158.3, 145.9, 144.5, 136.9, 128.9, 127.7, 125.9, 120.6, 114.1, 113.9, 95.3, 60.3, 55.4, 55.3, 37.5, 34.3; LC/MS-MS: 389.2→323.0 m/z; GS1 and GS2 at 30, DP=66, CE=29, CXP=22, tR=3.94 min.

Workup

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

Sources & evidence

ORD record
ord-4c73e0af3166445a81bd6730d8f63651
Source dataset
uspto-grants-2016_05
Patent number
US09353121B2

Reaction notes

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