Hydrochloric Acid → 5-Ethyl-7-hydroxy-8-methoxy-benzo[c]phenanthridinium hydrogen sulfate

HRID 1289025Notes

Reaction equation

HRID 1289025 reaction equation
C([O:8][C:9]1[C:10]2[C:19]([CH:20]=[CH:21][C:22]=1[O:23][CH3:24])=[C:18]1[C:13]([C:14]3[CH:28]=[CH:27][CH:26]=[CH:25][C:15]=3[CH:16]=[CH:17]1)=[N:12][CH:11]=2)C1C=CC=CC=1.FC(F)(F)S(O[CH2:35][CH3:36])(=O)=O.Cl.[S:40](=[O:44])(=[O:43])([OH:42])[OH:41]>CO.C(O)(=O)C.C1(C)C=CC=CC=1>[S:40]([O-:44])([OH:43])(=[O:42])=[O:41].[CH2:35]([N+:12]1[CH:11]=[C:10]2[C:19]([CH:20]=[CH:21][C:22]([O:23][CH3:24])=[C:9]2[OH:8])=[C:18]2[C:13]=1[C:14]1[CH:28]=[CH:27][CH:26]=[CH:25][C:15]=1[CH:16]=[CH:17]2)[CH3:36]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1118Sulfuric AcidHCID 67924Ethyl trifluoromethanesulphonateHCID 140378137-Benzyloxy-8-methoxybenzo[c]phenanthridine

Product 1

HCID 217375495-Ethyl-7-hydroxy-8-methoxy-benzo[c]phenanthridinium hydrogen sulfateYield 79.7%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

183 mg (0.5 mmol) of 7-benzyloxy-8-methoxybenzo[c]phenanthridine (compound D-7) were admixed with 0.13 ml (1.0 mmol) of ethyl trifluoromethanesulfonate and 0.9 ml of dry toluene, and the resulting mixture was heated to 100° C. for 5 hours. After that, the mixture was admixed with 4 ml of acetic acid and 1 ml of concentrated hydrochloric acid, and heated to 100° C. for 1 hour. Thereafter, the reaction mixture was gradually added to ice water. The reaction mixture thus diluted was neutralized by portionwise adding thereto sodium hydrogen carbonate, and then extracted with chloroform. The chloroform extract layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The resultant residue was refined by a silica gel chromatography, wherein use was made, as eluant, of a chloroform-methanol mixture (9:1). The main fractions were collected and concentrated to obtain a dark violet solid material, which was compound E-7 having a structure represented by the general formula E. Next, compound E-7 was dissolved in a small amount of methanol, and the solution thus obtained was acidified by portionwise adding thereto a dilute aqueous solution of sulfuric acid in an amount of from 1.0 to 2.0 mol per 1 mol of the compound, so that the color of the solution of the compound was changed into yellow or orange. The aqueous solution of the compound was then concentrated under reduced pressure. Acetone was added portionwise to the concentrated solution under shaking to form a precipitate, which was separated by filtration, and dried, so that the aimed compound A-7, wherein X- =HSO4-, was obtained as yellow powder in an amount of 160 mg (yield: 79.7%).

Workup

  1. temperatureheated to 100° C. for 1 hour
  2. additionThe reaction mixture thus diluted
  3. additionby portionwise adding
  4. extractionsodium hydrogen carbonate, and then extracted with chloroform
  5. extractionThe chloroform extract layer
  6. dry with materialwas dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe main fractions were collected
  10. concentrationconcentrated
  11. customto obtain a dark violet solid material, which
  12. customthe solution thus obtained
  13. additionby portionwise adding
  14. concentrationThe aqueous solution of the compound was then concentrated under reduced pressure
  15. additionAcetone was added portionwise to the concentrated solution
  16. customto form a precipitate, which
  17. customwas separated by filtration
  18. dry with materialdried, so that the aimed compound A-7, wherein X- =HSO4-
  19. customwas obtained as yellow powder in an amount of 160 mg (yield: 79.7%)

Sources & evidence

ORD record
ord-3088c6804ada4e52b2c9c27854f2da38
Source dataset
uspto-grants-1998_05
Patent number
US05747502

Reaction notes

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