Carbon Dioxide → 2-Methyl-5-nitroquinoline

HRID 2220238

Reaction equation

HRID 2220238 reaction equation
[CH3:1][C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[N:3]=1.[N+:12]([O-])([OH:14])=[O:13].C(=O)=O.[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[K+].[OH-].[Na+].O.N>S(=O)(=O)(O)O>[CH3:1][C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[CH:7][C:8]=2[N+:12]([O-:14])=[O:13])[N:3]=1

Participants

9

Reactant 7

HCID 280Carbon DioxideHCID 943NitrateHCID 944Nitric AcidHCID 70602-MethylquinolineHCID 14798Sodium HydroxideHCID 24434Potassium NitrateHCID 12896473Azane;hydrate

Product 1

HCID 2948672-Methyl-5-nitroquinoline

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

2-Methylquinoline (108.3 ml, 0.80 mol) is added in drops to 65% nitric acid (61 ml, 0.88 mol) at an internal temperature of 0-10° C. (dry ice cooling) within 45 minutes. After 1 hour, the precipitated nitrate is suctioned off and introduced in portions at an internal temperature of 0-6° C. in concentrated sulfuric acid (240 ml). After 30 minutes, potassium nitrate (6 g, 60 mmol) is added thereto, and it is stirred for 16 hours at room temperature. The batch is slowly poured onto ice/water, and a pH of 1.5 is set with 40% NaOH (˜500 ml). The precipitate is suctioned off, the filtrate is made alkaline with 25% ammonia water (pH 10) and filtered. The filter residue is dissolved in hot methanol (500 ml). During cooling, the 8-nitro-isomer crystallizes out. The mother liquor is concentrated by evaporation and purified by column chromatography on silica gel with hexane-ethyl acetate, whereby 53 g of the 2-methyl-5-nitroquinoline accumulates.

Workup

  1. waitAfter 30 minutes
  2. additionThe batch is slowly poured onto ice/water
  3. filtrationfiltered
  4. dissolutionThe filter residue is dissolved in hot methanol (500 ml)
  5. temperatureDuring cooling
  6. customthe 8-nitro-isomer crystallizes out
  7. concentrationThe mother liquor is concentrated by evaporation
  8. custompurified by column chromatography on silica gel with hexane-ethyl acetate, whereby 53 g of the 2-methyl-5-nitroquinoline

Sources & evidence

ORD record
ord-2b3023a3a5554417b4edaac830ddc58f
Source dataset
uspto-grants-2008_08
Patent number
US07417056B2

Linked notes

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