Benzaldehyde → HCID 89646463, compound

HRID 531194Notes

Reaction equation

HRID 531194 reaction equation
[CH:1](=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:9](#[N:13])[CH2:10][C:11]#[N:12].C(N(CC)CC)C.[CH3:21][O:22][C:23]1[CH:28]=[CH:27][C:26]([C:29]2[CH2:33][C:32](=[O:34])[N:31]([CH3:35])[N:30]=2)=[CH:25][CH:24]=1>C(O)C>[NH2:12][C:11]1[O:34][C:32]2[N:31]([CH3:35])[N:30]=[C:29]([C:26]3[CH:25]=[CH:24][C:23]([O:22][CH3:21])=[CH:28][CH:27]=3)[C:33]=2[CH:1]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C:10]=1[C:9]#[N:13]

Participants

6

Reactant 4

HCID 240BenzaldehydeHCID 8010MalononitrileHCID 8471TriethylamineHCID 15145018HCID 15145018, compound

Product 1

HCID 89646463HCID 89646463, compoundYield 8%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of benzaldehyde (290 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 (583 mg, 2.87 mmol, 1 equ.). The reaction mixture was concentrated after 24 h. The crude material was purified by column chromatography (25% ethyl acetate in hexanes to 100% ethyl acetate), then re-crystallized from ethanol and washed with hexanes and ethanol to give 6-amino-3-(4-methoxyphenyl)-1-methyl-4-phenyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (80.9 mg, 8%, 0.226 mmol) as a yellow solid. 1H-NMR (400 MHz) DMSO: 7.42-7.40 (d, 2H), 7.23-7.21 (m, 2H), 7.15-7.13 (d, 3H), 7.06 (s, 1H), 6.77-6.75 (d, 2H), 4.93 (s, 1H), 3.76 (s, 3H), 3.69 (s, 3H), 13C-NMR (100 MHz) DMSO: 159.1, 159.0, 145.9, 144.8, 144.5, 128.8, 127.8, 127.7, 127.1, 125.8, 120.5, 113.9, 95.0, 59.9, 55.4, 38.2, 34.4; LC/MS-MS: 359.1→293.0 m/z; GS1 and GS2 at 30, DP=76, CE=31, CXP=20, tR=3.96 min.

Workup

  1. concentrationThe reaction mixture was concentrated after 24 h
  2. customThe crude material was purified by column chromatography (25% ethyl acetate in hexanes to 100% ethyl acetate)
  3. customre-crystallized from ethanol
  4. washwashed with hexanes and ethanol

Sources & evidence

ORD record
ord-cc821b87af1c4decb589942bc7a90422
Source dataset
uspto-grants-2016_05
Patent number
US09353121B2

Reaction notes

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