Trifluoroacetic acid → 7-(3-Hydroxypropyl)-8-benzyloxy-9-methoxy-naphtho[2,3-c]phenanthridine

HRID 635527Notes

Reaction equation

HRID 635527 reaction equation
[CH2:1]([O:8][C:9]1[C:30]2[C:13](=[CH:14][C:15]3[C:28]4[N:27]=[CH:26][C:25]5[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=5)[C:19]=4[CH:18]=[CH:17][C:16]=3[CH:29]=2)[CH:12]=[CH:11][C:10]=1[O:31][CH3:32])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.FC(F)(F)C(O)=O.Br[CH2:41][CH2:42][CH2:43][OH:44].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(=O)([O-])O.[Na+]>C(#N)C>[OH:44][CH2:43][CH2:42][CH2:41][C:29]1[C:16]2[CH:17]=[CH:18][C:19]3[C:20]4[C:25]([CH:26]=[N:27][C:28]=3[C:15]=2[CH:14]=[C:13]2[C:30]=1[C:9]([O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[C:10]([O:31][CH3:32])[CH:11]=[CH:12]2)=[CH:24][CH:23]=[CH:22][CH:21]=4

Participants

8

Reactant 6

HCID 6422Trifluoroacetic acidHCID 6547AzobisisobutyronitrileHCID 123083-Bromo-1-propanolHCID 123134Tris(trimethylsilyl)silaneHCID 516892Sodium BicarbonateHCID 212582408-Benzyloxy-9-methoxy-naphtho[2,3-c]phenanthridine

Product 1

HCID 212582247-(3-Hydroxypropyl)-8-benzyloxy-9-methoxy-naphtho[2,3-c]phenanthridineYield 31.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

8-Benzyloxy-9-methoxy-naphtho[2,3-c]phenanthridine (231 mg, 0.56 mmol) was suspended in acetonitrile (80 mL), and trifluoroacetic acid (43 μL, 0.56 mmol), 3-bromo-1-propanol (51 μL, 0.56 mmol) and tris(trimethylsilyl)silane (346 μL, 1.12 mmol) were added to the suspension. The mixture was stirred at 80° C. on an oil bath. After the suspended matter was dissolved, azobis(isobutyronitrile) (184 mg, 1.12 mmol) was added to the solution followed by heating under reflux. An hour later, the reaction mixture was cooled to room temperature. Saturated sodium hydrogencarbonate aqueous solution (50 mL) was added to the residue followed by extraction with methylene chloride. After the organic layer was washed with water and dried over anhydrous sodium sulfate, the solvent was distilled off in vacuo. The residue was passed through a silica gel column (eluted with 1% methanol-methylene chloride). The main fractions were collected and the solvent was distilled off in vacuo. The residue was dissolved in toluene (3 mL) and activated manganese dioxide (100 mg) was added to the solution. The mixture was stirred at room temperature for 90 minutes. Manganese dioxide was filtered off and the filtrate was concentrated in vacuo to provide crude 7-(3-hydroxypropyl)-8-benzyloxy-9-methoxy-naphtho[2,3-c]phenanthridine (83 mg) as brown dry mass.

Workup

  1. dissolutionAfter the suspended matter was dissolved
  2. temperatureby heating
  3. temperatureunder reflux
  4. temperatureAn hour later, the reaction mixture was cooled to room temperature
  5. extractionfollowed by extraction with methylene chloride
  6. washAfter the organic layer was washed with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. distillationthe solvent was distilled off in vacuo
  9. washThe residue was passed through a silica gel column (eluted with 1% methanol-methylene chloride)
  10. customThe main fractions were collected
  11. distillationthe solvent was distilled off in vacuo
  12. dissolutionThe residue was dissolved in toluene (3 mL)
  13. additionactivated manganese dioxide (100 mg) was added to the solution
  14. stirringThe mixture was stirred at room temperature for 90 minutes
  15. filtrationManganese dioxide was filtered off
  16. concentrationthe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-be0c3a1816bb4e519f722e499107db0a
Source dataset
uspto-grants-2001_02
Patent number
US06187783B1

Reaction notes

Loading…