Hydrochloric Acid → 3-Amino-1-phenyl-1H-pyrazole-4-carbonitrile

HRID 1961507Notes

Reaction equation

HRID 1961507 reaction equation
[NH2:1][C:2]1[C:6]([C:7]#[N:8])=[CH:5][NH:4][N:3]=1.[C:9]1(B(O)O)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.N1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.Cl.[CH2:25](Cl)Cl>C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[NH:1]([C:2]1[C:6]([C:7]#[N:8])=[CH:5][N:4]([C:19]2[CH:25]=[CH:23][CH:22]=[CH:21][CH:20]=2)[N:3]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[NH2:1][C:2]1[C:6]([C:7]#[N:8])=[CH:5][N:4]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[N:3]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 1049PyridineHCID 6344DichloromethaneHCID 66827Phenylboronic AcidHCID 178510443HCID 178510443, compound

Product 2

HCID 27742493-Amino-1-phenyl-1H-pyrazole-4-carbonitrileHCID 672543033-anilino-1-phenyl-1H-pyrazole-4-carbonitrile

Reagents, catalysts & solvents 1

HCID 8895Cupric acetateCatalyst

Procedure

3-amino-1H-pyrazole-4-carbonitrile (200 mg, 1.850 mmol), copper(II) acetate (504 mg, 2.78 mmol), phenylboronic acid (451 mg, 3.70 mmol) and pyridine (0.599 mL, 7.40 mmol) were stirred in DCM (20 mL) at room temperature overnight. 2 N HCl was added and the products extracted in EtOAc (×2). The combined organic extracts were washed with brine, dried over MgSO4 and concentrated in vacuo. Purification of the residue by MPLC (2-30% EtOAc-hexanes) gave 3-anilino-1-phenyl-1H-pyrazole-4-carbonitrile (A) as a yellow solid and 3-amino-1-phenyl-1H-pyrazole-4-carbonitrile (B) as a pale yellow solid. 5-amino-1-phenyl-1H-pyrazole-4-carbonitrile was also isolated.

Workup

  1. extractionthe products extracted in EtOAc (×2)
  2. washThe combined organic extracts were washed with brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customPurification of the residue by MPLC (2-30% EtOAc-hexanes)

Sources & evidence

ORD record
ord-373c8816e2fb4293a7ec3800604d42b7
Source dataset
uspto-grants-2013_04
Patent number
US08415346B2

Reaction notes

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