Isoamyl Nitrite → HCID 13714613, compound

HRID 1890771Notes

Reaction equation

HRID 1890771 reaction equation
N(OCCC(C)C)=O.[CH3:9][N:10]1[C:14](N)=[C:13]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:12]=[N:11]1.[CH3:21][S:22]SC>C(Cl)(Cl)Cl>[CH3:9][N:10]1[C:14]([S:22][CH3:21])=[C:13]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:12]=[N:11]1

Participants

5

Reactant 3

HCID 8053Isoamyl Nitrite2×HCID 12232Dimethyl DisulfideHCID 271299Ethyl 5-amino-1-methyl-1H-pyrazole-4-carboxylate

Product 1

HCID 13714613HCID 13714613, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Conditions

Temperature
20 °C

Procedure

Add isopentyl nitrite (0.5 mL, 3.75 mmol) to a stirred 5° C. solution of ethyl 1-methyl-5-amino-1H-pyrazole-4-carboxylate (1.69 g, 10.0 mmol) and dimethyl disulfide (1.79 mL, 20.0 mmol) in CHCl3 under nitrogen in a 3-necked flask equipped with a thermometer and a condenser. Allow the reaction to warm to 20° C. in a H2O bath, and treat with additional isopentyl nitrite (1.5 mL, 11.3 mmol) dropwise. After 15 min, remove the reaction from the 20° C. H2O bath (exotherm raises temperature to 50° C. over approximately 1 min). Stir at ambient temperature under N2 overnight. Wash with H2O, and separate the layers. Extract the aqueous layer with CHCl3, combine the organic layers, dry over MgSO4, filter, and concentrate under reduced pressure. Purify the residue by flash silica gel chromatography (gradient of 0 to 35% EtOAc in hexanes) to afford the title compound (1.94 g, 97%). ES/MS m/z 201.0 (M+1).

Workup

  1. customequipped with a thermometer and a condenser
  2. customthe reaction
  3. customremove
  4. customthe reaction from the 20° C
  5. custom(exotherm raises temperature to 50° C. over approximately 1 min)
  6. washWash with H2O
  7. customseparate the layers
  8. extractionExtract the aqueous layer with CHCl3
  9. dry with materialdry over MgSO4
  10. filtrationfilter
  11. concentrationconcentrate under reduced pressure
  12. customPurify the residue by flash silica gel chromatography (gradient of 0 to 35% EtOAc in hexanes)

Sources & evidence

ORD record
ord-a8bf846487fd47809ef8d70130c60c37
Source dataset
uspto-grants-2013_08
Patent number
US08507490B2

Reaction notes

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