Acetonitrile → HCID 178510444, compound

HRID 1025648Notes

Reaction equation

HRID 1025648 reaction equation
C(#N)C.[NH2:4][C:5]1[NH:9][N:8]=[CH:7][C:6]=1[C:10]#[N:11].C(N(CC)CC)C.Br[C:20]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>O1CCCC1>[C:20]([NH:4][C:5]1[C:6]([C:10]#[N:11])=[CH:7][NH:8][N:9]=1)([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)[C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 8471TriethylamineHCID 11692BromotriphenylmethaneHCID 855155-Amino-4-cyanopyrazole

Product 1

HCID 178510444HCID 178510444, compoundYield 63.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of dry acetonitrile (10 mL) and dry tetrahydrofuran (30 mL) was added 5-amino-1H-pyrazole-4-carbonitrile (1.0 g, 9.25 mmol) followed by triethylamine (1.08 mL, 1.74 mmol). The resulting suspension was allowed to stir at room temperature for five minutes and then cooled to 0° C. A solution of (bromomethanetriyl)tribenzene (1.89 g, 5.84 mmol) in dry tetrahydrofuran (10 mL) was added drop-wise via an addition funnel equipped with a nitrogen inlet, at such a rate that the temperature did not rise above 5° C. The addition funnel was then rinsed with dry tetrahydrofuran (5 mL) and the reaction mixture was stirred at 0° C. for 10 minutes, then allowed to warm to room temperature and stirred for 2 hours. The volatiles were removed in vacuo and residue was dissolved in EtOAc (150 mL) and washed once water (100 mL), once with saturated aqueous sodium chloride, dried over Na2SO4, filtered and concentrated in vacuo. The crude product was applied to an 80 g silica gel cartridge using methylene chloride, and the column was eluted with a 10-30% EtOAc/hexanes gradient. The product containing fractions were combined to give 3-(Trityl-amino)-1H-pyrazole-4-carbonitrile (1.3 g, 41%) as an off-white semi-crystalline solid.

Workup

  1. temperaturecooled to 0° C
  2. customequipped with a nitrogen inlet
  3. customdid not rise above 5° C
  4. washThe addition funnel was then rinsed with dry tetrahydrofuran (5 mL)
  5. stirringthe reaction mixture was stirred at 0° C. for 10 minutes
  6. temperatureto warm to room temperature
  7. stirringstirred for 2 hours
  8. customThe volatiles were removed in vacuo and residue
  9. dissolutionwas dissolved in EtOAc (150 mL)
  10. washwashed once water (100 mL)
  11. dry with materialonce with saturated aqueous sodium chloride, dried over Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo
  14. washthe column was eluted with a 10-30% EtOAc/hexanes gradient
  15. additionThe product containing fractions

Sources & evidence

ORD record
ord-4352b31b9c7041a1b9916fc11a80c36f
Source dataset
uspto-grants-2014_05
Patent number
US08729078B2

Reaction notes

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