8-Methoxy-2H-phenanthro[3,4-d][1,3]dioxole-5-carboxylic acid → HCID 19828989, compound

HRID 1762859Notes

Reaction equation

HRID 1762859 reaction equation
[C:1]([C:4]1[C:17]2[CH:16]=[CH:15][C:14]3[C:9](=[CH:10][CH:11]=[CH:12][C:13]=3[O:18]C)[C:8]=2[C:7]2[O:20][CH2:21][O:22][C:6]=2[CH:5]=1)([OH:3])=[O:2].Cl.N1C=CC=CC=1>Cl>[C:1]([C:4]1[C:17]2[CH:16]=[CH:15][C:14]3[C:9](=[CH:10][CH:11]=[CH:12][C:13]=3[OH:18])[C:8]=2[C:7]2[O:20][CH2:21][O:22][C:6]=2[CH:5]=1)([OH:3])=[O:2]

Participants

4

Reactant 2

HCID 1194658-Methoxy-2H-phenanthro[3,4-d][1,3]dioxole-5-carboxylic acidHCID 10176127Pyridinium chloride

Product 1

HCID 19828989HCID 19828989, compound

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

1.0 g. 1-carboxy-3,4-methylenedioxy-8-methoxyphenanthrene is melted with 2.0 g. pyridine hydrochloride in an oil bath at 170° C. and maintained at this temperature for 1 hour while gassing with nitrogen. After cooling, the solidified mass is taken up with 10 liters 5% hydrochloric acid and extracted three times with 10 liter amounts of chloroform. The extracts are combined, washed neutral with water and dried by filtering through silanised filter paper (Whatman 1 PS). After evaporation of the solvent at 30° C. on a rotary evaporator, the mixture of starting material and hydrolysate is esterified for separation by boiling under reflux for 3 hours with a mixture of 2.5 liters methanol and 0.1 liter concentrated sulphuric acid. The reaction mixture is then poured into 10 liters of water and the aqueous methanolic phase shaken out three times with 10 liter amounts of diisopropyl ether. The organic solvent, after having been washed several times with water, is extracted with 10 liters of sodium hydroxide solution, the methyl ester of the 8-methoxy compound remaining in the organic phase, whereas the 8-hydroxy compound is transferred into the aqueous phase, with simultaneous hydrolysis of the ester. After washing with fresh diisopropyl ether, the alkaline phase is acidified and shaken out several times with chloroform. The chloroform solution is dried over phase separation paper (Whatman 1 PS) and the solvent stripped off on a rotary evaporator, 1-carboxy-3,4-methylenedioxy-8-hydroxyphenanthrene remaining behind in solid form as a thin layer chromatographically-uniform compound.

Workup

  1. temperatureAfter cooling
  2. extractionextracted three times with 10 liter amounts of chloroform
  3. washwashed neutral with water
  4. customdried
  5. filtrationby filtering through silanised filter paper (Whatman 1 PS)
  6. customAfter evaporation of the solvent at 30° C.
  7. customon a rotary evaporator
  8. additionthe mixture of starting material and hydrolysate
  9. customis esterified for separation
  10. temperatureunder reflux for 3 hours with a mixture of 2.5 liters methanol and 0.1 liter concentrated sulphuric acid
  11. additionThe reaction mixture is then poured into 10 liters of water
  12. washThe organic solvent, after having been washed several times with water
  13. extractionis extracted with 10 liters of sodium hydroxide solution
  14. customis transferred into the aqueous phase, with simultaneous hydrolysis of the ester
  15. washAfter washing with fresh diisopropyl ether
  16. stirringshaken out several times with chloroform
  17. dry with materialThe chloroform solution is dried over phase separation paper (Whatman 1 PS)
  18. customthe solvent stripped off on a rotary evaporator, 1-carboxy-3,4-methylenedioxy-8-hydroxyphenanthrene remaining behind in solid form as a thin layer chromatographically-uniform compound

Sources & evidence

ORD record
ord-4c33b62d73c74e96aceb3a6b9440797a
Source dataset
uspto-grants-1989_05
Patent number
US04835178

Reaction notes

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