Phosphoric Acid → HCID 20259004, compound

HRID 1649425Notes

Reaction equation

HRID 1649425 reaction equation
C(O[CH:4]=[C:5]([C:11]([O-:13])=O)[C:6]([O:8]CC)=[O:7])C.[Cl:14][C:15]1[CH:24]=[CH:23][CH:22]=[C:21]2[C:16]=1[CH2:17][CH2:18][CH:19]([CH3:25])[NH:20]2.P(=O)(O)(O)O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.[OH-].[Na+]>O.C(O)C>[Cl:14][C:15]1[C:16]2=[C:21]3[N:20]([CH:19]([CH3:25])[CH2:18][CH2:17]2)[CH:4]=[C:5]([C:6]([OH:8])=[O:7])[C:11](=[O:13])[C:22]3=[CH:23][CH:24]=1

Participants

8

Reactant 5

HCID 1004Phosphoric AcidHCID 14798Sodium HydroxideHCID 14812Phosphorus oxide (P4O10)HCID 20479711HCID 20479711, compoundHCID 858292113-Ethoxy-2-ethoxycarbonylprop-2-enoate

Product 1

HCID 20259004HCID 20259004, compoundYield 68.5%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

25 g of ethyl ethoxymethylenemalonate was added to 21 g of 5-chloro-2-methyl-1,2,3,4-tetrahydroquinoline and the mixture was heated on an oil bath at 110° to 120° C. during which time distillation of ethanol was observed. After heating the mixture at the same temperature as above for 30 minutes 160 g of polyphosphoric acid prepared from 80 g of phosphoric acid and 80 g of phosphorus pentoxide was added thereto followed by heating on an oil bath at 130° to 140° C. for 1 hour. After completion of the reaction the reaction mixture was poured into 600 ml of water and the resulting mixture was rendered neutral with a 10% aqueous sodium hydroxide solution to precipitate crystals, which were collected by filtration and mixed with 200 ml of a 10% aqueous sodium hydroxide solution and the mixture was heat-refluxed for 1 hour 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 pH was adjusted with concentrated hydrochloric acid to a pH of 2 to precipitate crystals. Recrystallization of the crude crystals thus-obtained from dimethylformamide gave 22 g of 8-chloro-5-methyl-6,7-dihydro-1-oxo-1H,5H-benzo-[ij]quinolizine-2-carboxylic acid as colorless rhombic crystals having a melting point of 290° to 291° C.

Workup

  1. additionwas added
  2. temperatureby heating on an oil bath at 130° to 140° C. for 1 hour
  3. customAfter completion of the reaction the reaction mixture
  4. customto precipitate crystals, which
  5. filtrationwere collected by filtration
  6. additionmixed with 200 ml of a 10% aqueous sodium hydroxide solution
  7. temperaturethe mixture was heat-refluxed for 1 hour during which time the crystals
  8. dissolutionwere dissolved
  9. customto form a uniform solution
  10. additionThe solution was treated with activated carbon while hot and
  11. filtrationfiltered
  12. temperatureto cool
  13. customto precipitate crystals
  14. customRecrystallization of the crude crystals
  15. customthus-obtained from dimethylformamide

Sources & evidence

ORD record
ord-9c31363e2c8740d8a7ffc106e44257d1
Source dataset
uspto-grants-1983_11
Patent number
US04416884

Reaction notes

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