Phosphoric Acid → 8-methanesulfonyloxy-6,7-dihydro-1-oxo-1H,5H-benzo[ij]quinolizine-2-carboxylic acid

HRID 2058498Notes

Reaction equation

HRID 2058498 reaction equation
C(O[CH:4]=[C:5]([C:11]([O-:13])=O)[C:6]([O:8]CC)=[O:7])C.[CH3:14][S:15]([O:18][C:19]1[CH:28]=[CH:27][CH:26]=[C:25]2[C:20]=1[CH2:21][CH2:22][CH2:23][NH:24]2)(=[O:17])=[O:16].P(=O)(O)(O)O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.[OH-].[Na+]>O.C(O)C>[CH3:14][S:15]([O:18][C:19]1[C:20]2=[C:25]3[N:24]([CH2:23][CH2:22][CH2:21]2)[CH:4]=[C:5]([C:6]([OH:8])=[O:7])[C:11](=[O:13])[C:26]3=[CH:27][CH:28]=1)(=[O:16])=[O:17]

Participants

8

Reactant 5

HCID 1004Phosphoric AcidHCID 14798Sodium Hydroxide2×HCID 14812Phosphorus oxide (P4O10)HCID 128996785-Methanesulfonyloxy-1,2,3,4-tetrahydroquinolineHCID 858292113-Ethoxy-2-ethoxycarbonylprop-2-enoate

Product 1

HCID 128996808-methanesulfonyloxy-6,7-dihydro-1-oxo-1H,5H-benzo[ij]quinolizine-2-carboxylic acidYield 66.8%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
110 °C

Procedure

21.6 g of ethyl ethoxymethylenemalonate was added to 22.4 g of 5-methanesulfonyloxy-1,2,3,4-tetrahydroquinoline and the mixture was heated at 110° C. on an oil bath for 30 minutes while stirring, during which time distillation of ethanol was observed. After heating, 240 g of polyphosphoric acid prepared from 120 g of phosphoric acid and 120 g of phosphorus pentoxide was added to the mixture and the mixture was allowed to react on an oil bath at 140° C. for 45 minutes. After completion of the reaction, the mixture was allowed to cool to room temperature and poured into 400 ml of water, followed by rendering the mixture neutral with 40% aqueous sodium hydroxide to precipitate crystals. The crystals thus-obtained were mixed with 150 ml of a 10% aqueous sodium hydroxide solution and the mixture was heat-refluxed for 40 minutes during which time the crystals were dissolved to form a uniform solution. The solution was treated with activated carbon while hot and filtered. The filtrate was allowed to cool and adjusted to a pH of 2 to precipitate crystals which were filtered. Recrystallization of the crude crystals thus-obtained from dimethylformamide gave 21.3 g of 8-methanesulfonyloxy-6,7-dihydro-1-oxo-1H,5H-benzo[ij]quinolizine-2-carboxylic acid as white needles having a melting point of 270° to 275° C.

Workup

  1. temperatureAfter heating
  2. additionwas added to the mixture
  3. customto react on an oil bath at 140° C. for 45 minutes
  4. customAfter completion of the reaction
  5. temperatureto cool to room temperature
  6. customto precipitate crystals
  7. customThe crystals thus-obtained
  8. temperaturethe mixture was heat-refluxed for 40 minutes during which time the crystals
  9. dissolutionwere dissolved
  10. customto form a uniform solution
  11. additionThe solution was treated with activated carbon while hot and
  12. filtrationfiltered
  13. temperatureto cool
  14. customto precipitate crystals which
  15. filtrationwere filtered
  16. customRecrystallization of the crude crystals
  17. customthus-obtained from dimethylformamide

Sources & evidence

ORD record
ord-8489d079bf0e40c88e1f11a87df16b08
Source dataset
uspto-grants-1982_03
Patent number
US04317820

Reaction notes

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