3-Methylisoquinoline → 3-Methyl-5-nitroisoquinoline

HRID 1911271Notes

Reaction equation

HRID 1911271 reaction equation
[CH3:1][C:2]1[N:3]=[CH:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[CH:7][CH:6]=2.[N+:12]([O-])([O-:14])=[O:13].[K+].[OH-].[Na+]>S(=O)(=O)(O)O>[CH3:1][C:2]1[N:3]=[CH:4][C:5]2[C:10]([CH:11]=1)=[C:9]([N+:12]([O-:14])=[O:13])[CH:8]=[CH:7][CH:6]=2

Participants

5

Reactant 3

HCID 143063-MethylisoquinolineHCID 14798Sodium HydroxideHCID 24434Potassium Nitrate

Product 1

HCID 2749733-Methyl-5-nitroisoquinolineYield 42%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
0 °C

Procedure

To a 0° C. solution of 3-methylisoquinoline (3.00 g, 20.9 mmol) in concentrated sulfuric acid (35 mL) was added solid potassium nitrate (2.33 g, 23.0 mmol) in four portions. The mixture was stirred 2 hours at 0° C. then was diluted with ice. This mixture was basified (pH 10) with 50% aqueous NaOH extracted with CH2Cl2 (60 mL). The organic phase was washed with brine (25 mL), dried (Na2SO4), filtered, and the volatiles were removed in vacuo. The resulting solid was triturated with 1:1 EtOAc-hexanes, filtered and air-dried to provide the title compound (1.60, 8.78 mmol, 42%) as a yellow solid. 1H NMR (300 MHz, CDCl3) δ 9.30 (s, 1H), 8.53 (dd, J=7.7, 1.1 Hz, 1H), 8.35 (s, 1H), 8.26 (d, J=8.1 Hz, 1H), 7.64 (dd, J=9.9, 5.9 Hz, 1H), 2.80 (s, 3H); MS (ESI) m/z 189 (M+H)+.

Workup

  1. additionthen was diluted with ice
  2. extractionextracted with CH2Cl2 (60 mL)
  3. washThe organic phase was washed with brine (25 mL)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. customthe volatiles were removed in vacuo
  7. customThe resulting solid was triturated with 1:1 EtOAc-hexanes
  8. filtrationfiltered
  9. customair-dried

Sources & evidence

ORD record
ord-c5bf2a12c14f4bfbbf7d69968e85ea8d
Source dataset
uspto-grants-2013_12
Patent number
US08604053B2

Reaction notes

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