Sodium hydride → 4-[(E)-2-cyanoethenyl]-1-[2-(trityloxy)ethyl]-5-aminopyrazole

HRID 349552Notes

Reaction equation

HRID 349552 reaction equation
[H-].[Na+].C(OP([CH2:11][C:12]#[N:13])(=O)OCC)C.[C:14]1([C:20]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[O:21][CH2:22][CH2:23][N:24]2[C:28]([NH2:29])=[C:27]([CH:30]=O)[CH:26]=[N:25]2)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>O1CCCC1>[C:12](/[CH:11]=[CH:30]/[C:27]1[CH:26]=[N:25][N:24]([CH2:23][CH2:22][O:21][C:20]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=2)[C:28]=1[NH2:29])#[N:13]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 179619611-(2-Triphenylmethyloxyethyl)-5-aminopyrazole-4-carbaldehyde

Product 1

HCID 179619694-[(E)-2-cyanoethenyl]-1-[2-(trityloxy)ethyl]-5-aminopyrazole

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of sodium hydride (60% dispersion in mineral oil, 3.46 g) in tetrahydrofuran (250 ml) was added dropwise diethyl(cyanomethyl)phosphonate (23.3 ml) under ice-cooling. The mixture was stirred under ice-cooling for 1 hour. To the reaction mixture was added a solution of 1-(2-triphenylmethyloxyethyl)-5-aminopyrazole-4-carbaldehyde (47.76 g) in tetrahydrofuran (250 ml) at room temperature. The mixture was stirred at room temperature for 5 hours and extracted with ethyl acetate. The extract was washed with aqueous sodium hydrogencarbonate solution, water and brine. The extract was dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The residue was triturated with diisopropyl ether and dried in vacuo to give 4-[(E)-2-cyanoethenyl]-1-[2-(trityloxy)ethyl]-5-aminopyrazole (59.38 g). 1H-NMR(DMSO-d6) δ3.13 (2H, t, J=4.9 Hz), 4.15 (2H, t, J=4.9 Hz), 5.59 (1H, d, J=16.3 Hz), 6.35 (2H, s), 7.0–7.4 (15H, m), 7.47 (1H, d, J=16.3 Hz), 7.63 (1H, s)

Workup

  1. temperaturecooling
  2. temperaturecooling for 1 hour
  3. stirringThe mixture was stirred at room temperature for 5 hours
  4. extractionextracted with ethyl acetate
  5. washThe extract was washed with aqueous sodium hydrogencarbonate solution, water and brine
  6. dry with materialThe extract was dried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was triturated with diisopropyl ether
  10. customdried in vacuo

Sources & evidence

ORD record
ord-b4f06b8e10e741989f141c5e6d2ccb57
Source dataset
uspto-grants-2007_02
Patent number
US07179801B2

Reaction notes

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