Methylhydrazine → Ethyl 1,4,4-trimethyl-7-oxo-4,5,6,7-tetrahydro-1H-indazole-3-carboxylate

HRID 44587Notes

Reaction equation

HRID 44587 reaction equation
C[O:2][C:3]1[C:4](=O)[CH:5]([C:11](=O)[C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:6]([CH3:10])([CH3:9])[CH2:7][CH:8]=1.[CH3:19][NH:20][NH2:21]>C(O)(=O)C.O>[CH3:19][N:20]1[C:4]2[C:3](=[O:2])[CH2:8][CH2:7][C:6]([CH3:10])([CH3:9])[C:5]=2[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[N:21]1

Participants

5

Reactant 2

HCID 6061MethylhydrazineHCID 57444091HCID 57444091, compound

Product 1

HCID 44235648Ethyl 1,4,4-trimethyl-7-oxo-4,5,6,7-tetrahydro-1H-indazole-3-carboxylateYield 47.7%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

A solution of ethyl (3-methoxy-6,6-dimethyl-2-oxocyclohex-3-en-1-yl)(oxo)acetate from the previous step (40.2 mmol theoretically) in acetic acid (65 mL) was treated dropwise with a solution of methyl hydrazine (2.14 mL, 40.2 mmol) in acetic acid (20 mL) and allowed to stand at room temperature overnight. The mixture was then diluted with water (800 mL) and extracted with ethyl acetate (500 mL×2). The organic extracts were washed with brine, dried on Na2SO4 and evaporated to dryness. The crude material was chromatographed on silica gel eluted with dichloromethane/ethyl acetate 100:5 to obtain the pure title compound (4.8 g, 47.7% yield).

Workup

  1. extractionextracted with ethyl acetate (500 mL×2)
  2. washThe organic extracts were washed with brine
  3. customdried on Na2SO4
  4. customevaporated to dryness
  5. customThe crude material was chromatographed on silica gel
  6. washeluted with dichloromethane/ethyl acetate 100:5

Sources & evidence

ORD record
ord-a64c308034a248aaa773faa85b468c4d
Source dataset
uspto-grants-2013_09
Patent number
US08541429B2

Reaction notes

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