Dimethyl Sulfate → HCID 10589184, compound

HRID 969593Notes

Reaction equation

HRID 969593 reaction equation
[H-].[Na+].[CH2:3]([C:6]#[N:7])[C:4]#[N:5].[N+:8]([C:11]1[CH:19]=[CH:18][C:14]([C:15](Cl)=O)=[CH:13][CH:12]=1)([O-:10])=[O:9].S(OC)(OC)(=O)=O.C(N(CC)CC)C.Cl.[C:35]([NH:39][NH2:40])([CH3:38])([CH3:37])[CH3:36]>O1CCCC1>[NH2:5][C:4]1[N:39]([C:35]([CH3:38])([CH3:37])[CH3:36])[N:40]=[C:15]([C:14]2[CH:18]=[CH:19][C:11]([N+:8]([O-:10])=[O:9])=[CH:12][CH:13]=2)[C:3]=1[C:6]#[N:7]

Participants

8

Reactant 6

HCID 6497Dimethyl SulfateHCID 8010MalononitrileHCID 8471TriethylamineHCID 85024-Nitrobenzoyl chlorideHCID 24758Sodium hydrideHCID 81889tert-Butylhydrazine monohydrochloride

Product 1

HCID 10589184HCID 10589184, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of sodium hydride (4.80 g, 0.2 mol, 2 eq, 60% dispersion in mineral oil) in tetrahydrofuran (100 mL) was slowly added malonodinitrile (6.61 g, 0.1 mol). 4-Nitrobenzoyl chloride (18.8 g, 0.1 mol, 1 eq) was then added in portions while keeping the reaction temperature below 10° C. The reaction mixture was stirred for 1 hour at room temperature. Dimethyl sulfate (15.1 g, 0.12 mol, 1.2 eq) was then added and the reaction mixture was refluxed for 2 hours. Triethylamine (25.3 g, 0.25 mol, 2.5 eq), followed by tert-butyl hydrazine hydrochloride (12.4 g, 10 mmol), was added and the reaction mixture was heated under reflux for an additional hour. The solvent was then evaporated and 50 mL of ethanol were added. The reaction mixture was heated under reflux, and water (250 mL) was added while keeping the temperature above 50° C. The reaction mixture was then cooled to 10° C. and 5-amino-1-tert-butyl-3-(4-nitro-phenyl)-1H-pyrazole-4-carbonitrile was isolated by filtration. 1H-NMR (DMSO-d6): ppm 1.59 (s, 9H), 6.55 (br s, 2H), 8.05 (d, 2H, J=7.2 Hz), 8.33 (d, 2H, J=7.2 Hz). LC MS (m/e)=285.8 (MH+).

Workup

  1. customthe reaction temperature below 10° C
  2. temperaturethe reaction mixture was refluxed for 2 hours
  3. additionwas added
  4. temperaturethe reaction mixture was heated
  5. temperatureunder reflux for an additional hour
  6. customThe solvent was then evaporated
  7. addition50 mL of ethanol were added
  8. temperatureThe reaction mixture was heated
  9. temperatureunder reflux
  10. additionwater (250 mL) was added
  11. customthe temperature above 50° C
  12. temperatureThe reaction mixture was then cooled to 10° C.

Sources & evidence

ORD record
ord-589dc80c55fc4f2fa158976d31573aac
Source dataset
uspto-grants-2007_12
Patent number
US07307097B2

Reaction notes

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