Malononitrile → 6-Amino-4-(4-fluorophenyl)-1,3-diphenyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile

HRID 531198Notes

Reaction equation

HRID 531198 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.[C:22]1([N:28]2[C:32](=[O:33])[CH2:31][C:30]([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)=[N:29]2)[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>C(O)C>[NH2:13][C:12]1[O:33][C:32]2[N:28]([C:22]3[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=3)[N:29]=[C:30]([C:34]3[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=3)[C:31]=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 785593H-Pyrazol-3-one, 2,4-dihydro-2,5-diphenyl-

Product 1

HCID 896500416-Amino-4-(4-fluorophenyl)-1,3-diphenyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrileYield 20.5%

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 1,3-diphenyl-1H-pyrazol-5(4H)-one (678 mg, 2.87 mmol, 1 equ.). The precipitate formed was filtered out and washed with ethanol and hexanes, and re-crystallized from ethanol to afford 6-amino-4-(4-fluorophenyl)-1,3-diphenyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (240 mg, 0.588 mmol, 20%) as a white powder. 1H-NMR (400 MHz) DMSO: 7.94-7.92 (d, 2H), 7.61-7.55 (m, 4H), 7.42-7.38 (t, 1H), 7.28-7.24 (m, 7H), 7.06-7.02 (t, 2H), 5.15 (s, 1H), 13C-NMR (100 MHz) DMSO: 162.6, 159.0, 146.8, 145.6, 140.6, 137.8, 132.5, 130.0, 129.9, 129.8, 128.6, 128.6, 127.3, 127.0, 121.3, 120.2, 115.6, 115.4, 97.9, 59.6, 37.0; LC/MS-MS: 410.4→242.2 m/z; GS1 and GS2 at 30, DP=21, CE=47, CXP=16, tR=4.63 min.

Workup

  1. customThe precipitate formed
  2. filtrationwas filtered out
  3. washwashed with ethanol and hexanes
  4. customre-crystallized from ethanol

Sources & evidence

ORD record
ord-2f50aac3036843c5a53f6279be94ea46
Source dataset
uspto-grants-2016_05
Patent number
US09353121B2

Reaction notes

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