Tert-Butyl nitrite → 3-Methyl-6-nitro-1H-indazole

HRID 1640700Notes

Reaction equation

HRID 1640700 reaction equation
[CH2:1]([C:3]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[CH:6][C:4]=1[NH2:5])[CH3:2].[N:13](OC(C)(C)C)=O>C(O)(=O)C.C(OCC)(=O)C>[CH3:2][C:1]1[C:3]2[C:4](=[CH:6][C:7]([N+:10]([O-:12])=[O:11])=[CH:8][CH:9]=2)[NH:5][N:13]=1

Participants

5

Reactant 2

HCID 10906Tert-Butyl nitriteHCID 41554782-Ethyl-5-nitroaniline

Product 1

HCID 109210543-Methyl-6-nitro-1H-indazoleYield 98%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 10 g (0.06 mol) of 2-ethyl-5-nitroaniline (prepared by nitration of 2-ethylaniline: Bergman and Sand, Tetrahedron 1990, 46, 6085-6112) in 300 ml of glacial acetic acid, at room temperature, was added a solution of 8.98 ml (0.06 mol) of tert-butyl nitrite in 40 ml of acetic acid dropwise over 15 min. After the addition was complete the solution was allowed to stir for 30 min. The acetic acid was removed in vacuo to afford an orange solid. The solid was dissolved in approximately 120 ml of ethyl acetate and washed with 3×100 ml sat. aqueous NaHCO3. The organic layer was dried over MgSO4 and the solvent was removed in vacuo to afford 3-methyl-6-nitroindazole as a yellow solid (10.4 g, 98%).

Workup

  1. additionAfter the addition
  2. customThe acetic acid was removed in vacuo
  3. customto afford an orange solid
  4. washwashed with 3×100 ml sat. aqueous NaHCO3
  5. dry with materialThe organic layer was dried over MgSO4
  6. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-ca29a5adbebf40819822caefb18de5e9
Source dataset
uspto-grants-2012_02
Patent number
US08114885B2

Reaction notes

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