Trifluoroacetic acid → HCID 15518230, compound

HRID 635521Notes

Reaction equation

HRID 635521 reaction equation
[CH2:1]1[O:31][C:4]2=[CH:5][C:6]3[C:19]4[C:10](=[C:11]5[C:16](=[CH:17][N:18]=4)[C:15]([O:20][CH2:21][C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)=[C:14]([O:28][CH3:29])[CH:13]=[CH:12]5)[CH:9]=[CH:8][C:7]=3[CH:30]=[C:3]2[O:2]1.FC(F)(F)C(O)=O.Br[CH2:40][CH2:41][CH2:42][OH:43].C[Si]([SiH]([Si](C)(C)C)[Si](C)(C)C)(C)C.N(C(C)(C)C#N)=NC(C)(C)C#N>C(#N)C>[CH2:1]1[O:31][C:4]2=[CH:5][C:6]3[C:19]4[C:10](=[C:11]5[C:16](=[C:17]([CH2:40][CH2:41][CH2:42][OH:43])[N:18]=4)[C:15]([O:20][CH2:21][C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)=[C:14]([O:28][CH3:29])[CH:13]=[CH:12]5)[CH:9]=[CH:8][C:7]=3[CH:30]=[C:3]2[O:2]1

Participants

7

Reactant 5

HCID 6422Trifluoroacetic acidHCID 6547AzobisisobutyronitrileHCID 123083-Bromo-1-propanolHCID 123134Tris(trimethylsilyl)silaneHCID 10573555HCID 10573555, compound

Product 1

HCID 15518230HCID 15518230, compoundYield 15%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

2,3-(Methylenedioxy)-7-benzyloxy-8-methoxy-benzo[c]phenanthridine (prepared by the process described in Japanese Patent KOKAI No. 5-208959, 1.228 g, 3.00 mmols) was suspended in acetonitrile (48 mL), and trifluoroacetic acid (231 μL, 3.00 mmols), 3-bromo-1-propanol (271 μL, 3.00 mmols) and tris(trimethylsilyl)silane (1.85 mL, 6.00 mmols) were added to the suspension. The mixture was stirred at 80° C. on an oil bath. After the suspension was dissolved, azobis(isobutyronitrile) (0.985 g, 6.00 mmols) was added to the solution followed by heating under reflux. 90 minutes later, the reaction mixture was cooled to room temperature. By separating the precipitated crystals through filtration, the starting material, 2,3-(methylenedioxy)-7-benzyloxy-8-methoxy-benzo[c]phenanthridine, was recovered as the trifluoroacetate (0.680 g). The filtrate was concentrated in vacuo, and a saturated sodium hydrogencarbonate aqueous solution (40 mL) was added to the residue followed by extraction with methylene chloride (50 mL). After the organic layer was washed with water (50 mL) and dried over anhydrous sodium sulfate, the solvent was distilled off in vacuo. The residue was purified by silica gel column chromatography (eluted with 10% ethyl acetate-toluene) to give 2,3-(methylenedioxy)-6-(3-hydroxypropyl)-7-benzyloxy-8-methoxy-benzo[c]phenanthridine (0.210 g, yield 15%) as light brown powders.

Workup

  1. dissolutionAfter the suspension was dissolved
  2. temperatureby heating
  3. temperatureunder reflux
  4. temperature90 minutes later, the reaction mixture was cooled to room temperature
  5. customBy separating the precipitated crystals
  6. filtrationthrough filtration
  7. customthe starting material, 2,3-(methylenedioxy)-7-benzyloxy-8-methoxy-benzo[c]phenanthridine, was recovered as the trifluoroacetate (0.680 g)
  8. concentrationThe filtrate was concentrated in vacuo
  9. additiona saturated sodium hydrogencarbonate aqueous solution (40 mL) was added to the residue
  10. extractionfollowed by extraction with methylene chloride (50 mL)
  11. washAfter the organic layer was washed with water (50 mL)
  12. dry with materialdried over anhydrous sodium sulfate
  13. distillationthe solvent was distilled off in vacuo
  14. customThe residue was purified by silica gel column chromatography (eluted with 10% ethyl acetate-toluene)

Sources & evidence

ORD record
ord-c631c29fff864407ad4856a928ec26ca
Source dataset
uspto-grants-2001_02
Patent number
US06187783B1

Reaction notes

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