Ammonium Chloride → HCID 69422773, compound

HRID 349992Notes

Reaction equation

HRID 349992 reaction equation
C1(C)C=CC(S([CH2:10][N+:11]#[C-])(=O)=O)=CC=1.CC(C)([O-])C.[K+].[CH2:20]([O:27][C:28]1[CH:48]=[CH:47][C:31]([CH2:32][N:33]2[CH:37]=[C:36]([CH:38]=O)[C:35]([C:40]3[CH:45]=[CH:44][C:43]([F:46])=[CH:42][CH:41]=3)=[N:34]2)=[CH:30][CH:29]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[Cl-].[NH4+]>C(COC)OC.CO>[CH2:20]([O:27][C:28]1[CH:48]=[CH:47][C:31]([CH2:32][N:33]2[CH:37]=[C:36]([CH2:38][C:10]#[N:11])[C:35]([C:40]3[CH:45]=[CH:44][C:43]([F:46])=[CH:42][CH:41]=3)=[N:34]2)=[CH:30][CH:29]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 161915Tosylmethyl isocyanideHCID 23025043HCID 23025043, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 69422773HCID 69422773, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 80711,2-DimethoxyethaneSolvent3×

Procedure

A solution of p-toluenesulfonylmethylisocyanide (3.08 g) in dimethoxyethane (15 ml) was added to a mixture of potassium t-butoxide (3.37 g) and dimethoxyethane (15 ml) at −78° C., and the resultant was stirred for 5 minutes. A solution of 1-(4-benzyloxybenzyl)-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehyde (5.80 g) in dimethoxyethane (30 ml) was added to the mixture. After stirring at the same temperature, the mixture was stirred for 1 hour while raising the temperature. Methanol (45 ml) was added to the mixture, which was refluxed for 1 hour. After cooling, the reaction mixture was poured into saturated aqueous ammonium chloride solution, which was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium chloride solution, dried (MgSO4), and concentrated. The residue was subjected to silica gel column chromatography to obtain 1-(4-benzyloxybenzyl)-3-(4-fluorophenyl)-1H-pyrazol-4-ylacetonitrile (4.52 g, yield 76%) as colorless crystals from the fraction eluted with ethyl acetate-hexane (1:2, volume ratio). This was recrystallized from ethyl acetate-hexane. Melting point: 86–87° C.

Workup

  1. stirringAfter stirring at the same temperature
  2. stirringthe mixture was stirred for 1 hour
  3. temperaturewhile raising the temperature
  4. temperaturewas refluxed for 1 hour
  5. temperatureAfter cooling
  6. extractionwas extracted with ethyl acetate
  7. washThe ethyl acetate layer was washed with saturated aqueous sodium chloride solution
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-1ecd2f870cdf47258ddedd4122eecc76
Source dataset
uspto-grants-2007_02
Patent number
US07179823B1

Reaction notes

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