Malononitrile → HCID 89647247, compound

HRID 531201Notes

Reaction equation

HRID 531201 reaction equation
[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][CH:3]=1.[C:10](#[N:14])[CH2:11][C:12]#[N:13].C(N(CC)CC)C.[CH3:22][O:23][C:24]1[CH:29]=[CH:28][C:27]([C:30]2[CH2:34][C:33](=[O:35])[N:32]([CH3:36])[N:31]=2)=[CH:26][CH:25]=1>C(O)C>[NH2:13][C:12]1[O:35][C:33]2[N:32]([CH3:36])[N:31]=[C:30]([C:27]3[CH:26]=[CH:25][C:24]([O:23][CH3:22])=[CH:29][CH:28]=3)[C:34]=2[CH:6]([C:5]2[CH:8]=[CH:9][C:2]([F:1])=[CH:3][CH:4]=2)[C:11]=1[C:10]#[N:14]

Participants

6

Reactant 4

HCID 8010MalononitrileHCID 8471TriethylamineHCID 680234-FluorobenzaldehydeHCID 15145018HCID 15145018, compound

Product 1

HCID 89647247HCID 89647247, compoundYield 32.4%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 4-fluorobenzaldehyde (300 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 (586 mg, 2.87 mmol, 1 equ.). The reaction mixture was concentrated after 19 h and the precipitate formed was washed with ethanol and hexanes, re-crystallized from ethanol, and washed with hexanes and ethanol to give 6-amino-4-(4-fluorophenyl)-3-(4-methoxyphenyl)-1-methyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (350 mg, 0.930 mmol, 32%) as a white solid. 1H-NMR (400 MHz) DMSO: 7.43-7.40 (d, 2H), 7.20-7.16 (m, 2H), 7.10 (s, 2H), 7.06-7.02 (t, 2H), 6.78-6.76 (d, 2H), 4.99 (s, 1H), 3.75 (s, 3H), 3.69 (s, 3H), 13C-NMR (100 MHz) DMSO: 162.5, 159.1, 145.8, 144.6, 141.0, 141.0, 129.8, 129.7, 127.8, 125.7, 120.5, 115.6, 115.4, 113.9, 94.9, 59.7, 55.4, 3 7.4, 34.4; LC/MS-MS: 377.1→311.1 m/z; GS1 and GS2 at 30, DP=66, CE=33, CXP=20, tR=3.98 min.

Workup

  1. concentrationThe reaction mixture was concentrated after 19 h
  2. customthe precipitate formed
  3. washwas washed with ethanol and hexanes
  4. customre-crystallized from ethanol
  5. washwashed with hexanes and ethanol

Sources & evidence

ORD record
ord-2ca4f28e9c3440998d8d6de6212b2ad8
Source dataset
uspto-grants-2016_05
Patent number
US09353121B2

Reaction notes

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