HCID 66746823, compound → HCID 66746696, compound

HRID 1467049Notes

Reaction equation

HRID 1467049 reaction equation
[CH2:1]([O:5][C:6]1[CH:13]=[CH:12][CH:11]=[C:10]([N+:14]([O-])=O)[C:7]=1[C:8]#[N:9])[CH:2]([CH3:4])[CH3:3]>CC(O)=O.C1COCC1.CCOC(C)=O.[Fe]>[NH2:14][C:10]1[CH:11]=[CH:12][CH:13]=[C:6]([O:5][CH2:1][CH:2]([CH3:4])[CH3:3])[C:7]=1[C:8]#[N:9]

Participants

5

Reactant 1

HCID 66746823HCID 66746823, compound

Product 1

HCID 66746696HCID 66746696, compoundYield 83%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 8857Ethyl AcetateSolventHCID 23444217Acetic acid tetrahydrofuranSolvent

Procedure

To a solution of 2-isobutoxy-6-nitrobenzonitrile (Example 41c, 34.3 g, 0.156 mol) in AcOH/THF (1:1 by volume, 250 mL) was added iron powder (17.36 g, 0.311 mol) in one portion. The stirred suspension was heated to reflux for 30 minutes. After it was cooled down to room temperature, the reaction solution was diluted with EtOAc (1 L). The solid was removed by filtration, and the filtrate was washed subsequently with water (300 mL×2), 1N NaOH (300 mL), saturated Na2CO3 aqueous solution (300 mL), brine (300 mL), and dried over Na2SO4. After evaporation of the solvent, the residue was purified by chromatography on silica gel eluting with 20% EtOAc in hexanes to give the title compound as a yellow oil (16.4 g, 83%). 1H NMR (400 MHz, DMSO-d6) δ 0.96 (d, J=6.8 Hz, 6H), 1.96-2.02 (m, 1H), 3.75 (d, J=6.4 Hz, 2H), 5.96 (s, 2H), 6.17 (d, J=8.4 Hz, 1H), 6.30 (d, J=8.4 Hz, 1H), 7.15 (t, J=8.8 Hz, 1H). MS 191 (MH+).

Workup

  1. temperatureThe stirred suspension was heated
  2. temperatureto reflux for 30 minutes
  3. customThe solid was removed by filtration
  4. washthe filtrate was washed subsequently with water (300 mL×2), 1N NaOH (300 mL), saturated Na2CO3 aqueous solution (300 mL), brine (300 mL)
  5. dry with materialdried over Na2SO4
  6. customAfter evaporation of the solvent
  7. customthe residue was purified by chromatography on silica gel eluting with 20% EtOAc in hexanes

Sources & evidence

ORD record
ord-82edec2b4cc04857ab4923d68d80aad6
Source dataset
uspto-grants-2015_04
Patent number
US09000054B2

Reaction notes

Loading…