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Ammonium Chloride → (3-benzyloxy-1-phenyl-1H-pyrazol-4-yl)acetonitrile

HRID 1295251
Notes
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Reaction equation

HRID 1295251 reaction equation
CC(C)([O-])C.[K+].C1(C)C=CC(S([CH2:16][N+:17]#[C-])(=O)=O)=CC=1.[CH2:20]([O:27][C:28]1[C:32]([CH:33]=O)=[CH:31][N:30]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[N: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[C:32]([CH2:33][C:16]#[N:17])=[CH:31][N:30]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[N:29]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 161915Tosylmethyl isocyanideHCID 229307603-benzyloxy-1-phenyl-1H-pyrazole-4-carbaldehydeHCID 23665647Potassium tert-butoxide

Product 1

HCID 69430614(3-benzyloxy-1-phenyl-1H-pyrazol-4-yl)acetonitrileYield 67.3%

Reagents, catalysts & solvents 2

HCID 887
Methanol
Solvent
HCID 80711,2-DimethoxyethaneSolvent3×

Conditions

Temperature
-78 °C

Procedure

To a mixture of potassium t-butoxide (3.82 g) and dimethoxyethane (20 ml) was added a solution of p-toluenesulfonylmethyl isocyanide (3.51 g) in dimethoxyethane (20 ml) and the mixture was stirred at −78° C. for 5 min. Then a solution of 3-benzyloxy-1-phenyl-1H-pyrazole-4-carbaldehyde (4.73 g) in dimethoxyethane (80 ml) was added. After stirring at said temperature for 1 hr, the mixture was stirred for 1 hr. while raising the temperature to room temperature. To the obtained mixture was added methanol (100 ml), and the mixture was refluxed for 1 hr. After cooling, the reaction solution was poured into saturated aqueous ammonium chloride solution and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried (MgSO4) and concentrated. The residue was subjected to silica gel column chromatography, and 3-benzyloxy-1-phenyl-1H-pyrazol-4-ylacetonitrile (3.31 g, yield 67%). was obtained as colorless crystals from a fraction eluted with ethyl acetate-hexane (1:3, volume ratio). The crystals were recrystallized from tetrahydrofuran-hexane. melting point: 102–103° C.

Workup

  1. stirringAfter stirring
  2. customfor 1 hr
  3. stirringthe mixture was stirred for 1 hr
  4. temperaturewhile raising the temperature to room temperature
  5. temperaturethe mixture was refluxed for 1 hr
  6. temperatureAfter cooling
  7. extractionthe mixture was extracted with ethyl acetate
  8. washThe ethyl acetate layer was washed with saturated brine
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-f831f4b1a2db4a7aabf4698a52c5a21e
Source dataset
uspto-grants-2007_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07241785B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes