Triethyl Phosphate → 5-Chloro-2,6-dimethoxy-4-methyl-8-nitroquinoline

HRID 1018028Notes

Reaction equation

HRID 1018028 reaction equation
C(OP(OCC)(OCC)=O)C.[CH3:12][O:13][C:14]1[CH:23]=[C:22]([CH3:24])[C:21]2[C:16](=[CH:17][CH:18]=[C:19]([O:26][CH3:27])[C:20]=2[Cl:25])[N:15]=1.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.[N+:42]([O-])([O-:44])=[O:43].[K+]>CO>[N+:42]([C:17]1[CH:18]=[C:19]([O:26][CH3:27])[C:20]([Cl:25])=[C:21]2[C:16]=1[N:15]=[C:14]([O:13][CH3:12])[CH:23]=[C:22]2[CH3:24])([O-:44])=[O:43]

Participants

6

Reactant 4

HCID 6535Triethyl PhosphateHCID 14812Phosphorus oxide (P4O10)HCID 24434Potassium NitrateHCID 184059815-Chloro-2,6-dimethoxy-4-methylquinoline

Product 1

HCID 109680055-Chloro-2,6-dimethoxy-4-methyl-8-nitroquinolineYield 68%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
37.5 °C

Procedure

A 20-liter reactor equipped with a mechanical stirrer, thermowatch, and condenser was charged with triethylphosphate (6.3 liters) and 2,6-dimethoxy-5-chloro-4-methylquinoline (5) (500 g, 2.11 moles). Phosphorous pentoxide (1.052 kg, 7.11 moles) was added in one portion and the resulting slurry stirred for 60 minutes. Reaction temperature was adjusted to 35° C. and solid potassium nitrate (0.423 kg, 4.21 moles) added in one portion. N-hexane is added and the reaction temperature was maintained at 35-40° C. for 2 hours. Methanol (4.2 liters) was added and the mixture heated to reflux and held for 1 hour. The yellow slurry was cooled to 0-5° C. and held for 2 hours. The product was collected by suction filtration, washed with water to neutral pH, then methanol, air dried and oven dried at 60-70° C. to yield the title compound 350 g (68%); mp 199-200° C.;

Workup

  1. customA 20-liter reactor equipped with a mechanical stirrer
  2. customReaction temperature
  3. customwas adjusted to 35° C.
  4. temperaturethe mixture heated
  5. temperatureto reflux
  6. waitheld for 1 hour
  7. temperatureThe yellow slurry was cooled to 0-5° C.
  8. waitheld for 2 hours
  9. filtrationThe product was collected by suction filtration
  10. washwashed with water to neutral pH
  11. dry with materialmethanol, air dried
  12. customoven dried at 60-70° C.

Sources & evidence

ORD record
ord-a48012aecff44ec6833a918f6091d8d0
Source dataset
uspto-grants-2002_11
Patent number
US06479660B1

Reaction notes

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