2-(Ethoxymethylene)propanedinitrile → HCID 57438665, compound

HRID 1098242Notes

Reaction equation

HRID 1098242 reaction equation
[Br:1][C:2]1[C:3]([CH3:10])=[C:4]([NH:8][NH2:9])[CH:5]=[CH:6][CH:7]=1.C(O[CH:14]=[C:15]([C:18]#[N:19])[C:16]#[N:17])C.C(N(C(C)C)C(C)C)C>CO>[NH2:19][C:18]1[N:8]([C:4]2[CH:5]=[CH:6][CH:7]=[C:2]([Br:1])[C:3]=2[CH3:10])[N:9]=[CH:14][C:15]=1[C:16]#[N:17]

Participants

5

Reactant 3

HCID 671522-(Ethoxymethylene)propanedinitrileHCID 81531DiisopropylethylamineHCID 22595958HCID 22595958, compound

Product 1

HCID 57438665HCID 57438665, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

(3-Bromo-2-methylphenyl)hydrazine (CAS no. 459817-67-5) (10 g, 49.74 mmol) was suspended in MeOH (100 mL) under nitrogen at 0° C. 2-(Ethoxymethylene)malononitrile (6.07 g, 49.74 mmol) added portionwise over 5 mins and the mixture stirred at ˜0° C. for 2 hours. The reaction mixture was allowed to warm to room temperature and then heated at reflux under nitrogen for 2 hours. No reaction. The starting material was NMRed and found to be a salt, so N-ethyl-N-isopropylpropan-2-amine (17.33 mL, 99.47 mmol) was added and stirred for a further 16 hours. The reaction mixture was evaporated to dryness and redissolved in EtOAc, and washed sequentially with water ×2 and saturated brine. The organic layer was dried (MgSO4), filtered and evaporated to afford crude product, 5-amino-1-(3-bromo-2-methylphenyl)-1H-pyrazole-4-carbonitrile (12.60 g, 91%). m/z (ES+) (M+H)+=279.25; HPLC tR=1.95 min.

Workup

  1. temperatureto warm to room temperature
  2. temperatureheated
  3. temperatureat reflux under nitrogen for 2 hours
  4. customNo reaction
  5. additionwas added
  6. stirringstirred for a further 16 hours
  7. customThe reaction mixture was evaporated to dryness
  8. dissolutionredissolved in EtOAc
  9. washwashed sequentially with water ×2 and saturated brine
  10. dry with materialThe organic layer was dried (MgSO4)
  11. filtrationfiltered
  12. customevaporated

Sources & evidence

ORD record
ord-db7d6169d6c64033a398ccd2d5ad16d8
Source dataset
uspto-grants-2012_03
Patent number
US08143263B2

Reaction notes

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