Carbonate Ion → 5-Amino-1-(2-methyl-3-pyridinyl)-1H-pyrazole-4-carbonitrile

HRID 1098148Notes

Reaction equation

HRID 1098148 reaction equation
C(=O)([O-])[O-].Cl.[NH:6]([C:8]1[C:9]([CH3:14])=[N:10][CH:11]=[CH:12][CH:13]=1)[NH2:7].C(O[CH:18]=[C:19]([C:22]#[N:23])[C:20]#[N:21])C>C(Cl)Cl.CO>[NH2:23][C:22]1[N:6]([C:8]2[C:9]([CH3:14])=[N:10][CH:11]=[CH:12][CH:13]=2)[N:7]=[CH:18][C:19]=1[C:20]#[N:21]

Participants

6

Reactant 3

HCID 19660Carbonate IonHCID 671522-(Ethoxymethylene)propanedinitrileHCID 57438650HCID 57438650, compound

Product 1

HCID 574386515-Amino-1-(2-methyl-3-pyridinyl)-1H-pyrazole-4-carbonitrileYield 46.5%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

MP-carbonate (2.64 mmol/g) (2.6 g, 6.80 mmol) was added to 3-hydrazinyl-2-methylpyridine hydrochloride (Intermediate V2) (362 mg, 2.27 mmol) in DCM (10 mL). The reaction mixture was stirred at room temperature for 6 hours. The reaction mixture was filtered and evaporated. 2-(Ethoxymethylene)malononitrile (277 mg, 2.27 mmol) was added to suspension of the above solid in MeOH (6 mL) under nitrogen cooled to −5° C. The reaction mixture was stirred at 0° C. for 30 mins and then allowed to warm to room temperature and heated at reflux under nitrogen for 2 hours. The reaction mixture was allowed to cool and evaporated to dryness to afford the product (210 mg, 46.5%) which was used without further purification. 1H NMR (400 MHz, DMSO) δ 2.23 (3H, s), 6.65 (2H, s), 7.39-7.43 (1H, m), 7.74 (1H d), 7.79 (1H, s), 8.58-8.60 (1H, m), m/z (ESI+) (M+H)+=200; HPLC tR=1.21 min.

Workup

  1. filtrationThe reaction mixture was filtered
  2. customevaporated
  3. temperaturecooled to −5° C
  4. stirringThe reaction mixture was stirred at 0° C. for 30 mins
  5. temperatureto warm to room temperature
  6. temperatureheated
  7. temperatureat reflux under nitrogen for 2 hours
  8. temperatureto cool
  9. customevaporated to dryness

Sources & evidence

ORD record
ord-fe0bf515bc9949168d3d4cd356620c44
Source dataset
uspto-grants-2012_03
Patent number
US08143263B2

Reaction notes

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