Methanol → 8-Chloro-6-(2-chlorophenyl)-1-methoxy-4H-imidazo[1,5-a][1,4]benzodiazepine-3-carboxylic acid, methyl ester

HRID 261703Notes

Reaction equation

HRID 261703 reaction equation
[CH3:1][O:2][C:3]([C:5]1[N:6]=[C:7](Cl)[N:8]2[C:14]3[CH:15]=[CH:16][C:17]([Cl:19])=[CH:18][C:13]=3[C:12]([C:20]3C=[CH:24][CH:23]=[CH:22][C:21]=3Cl)=[N:11][CH2:10][C:9]=12)=[O:4].[CH3:28][O-:29].[Na+].CO.[CH:33]([Cl:36])(Cl)Cl>>[Cl:19][C:17]1[CH:16]=[CH:15][C:14]2[N:8]3[C:7]([O:29][CH3:28])=[N:6][C:5]([C:3]([O:2][CH3:1])=[O:4])=[C:9]3[CH2:10][N:11]=[C:12]([C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][C:33]=3[Cl:36])[C:13]=2[CH:18]=1

Participants

5

Reactant 4

HCID 887MethanolHCID 6212ChloroformHCID 10942334Sodium MethoxideHCID 541351956-(2-chlorophenyl)-1,8-dichloro-4H-imidazo[1,5-a][1,4]benzodiazepine-3-carboxylic acid methyl ester

Product 1

HCID 544751158-Chloro-6-(2-chlorophenyl)-1-methoxy-4H-imidazo[1,5-a][1,4]benzodiazepine-3-carboxylic acid, methyl ester

Procedure

A mixture of 2.9 g (0.007 mole) of 6-(2-chlorophenyl)-1,8-dichloro-4H-imidazo[1,5-a][1,4]benzodiazepine-3-carboxylic acid methyl ester, 1.1 g (0.02 mole) of sodium methoxide and 100 ml of dry methanol was heated in a steel bomb at 115°-120° for 20 hrs. The solvent was removed at reduced pressure. The residue was dissolved in methylene chloride, washed with dilute hydrochloric acid to give pale yellow amorphous solid. An ethereal solution (60 ml) of the solid was washed with dilute ammonium hydroxide solution, dried, filtered and concentrated on a steam bath to about 20 ml. White crystals were obtained after keeping the solution at room temperature for several hours with occasional scratching. Recrystallization from ether gave white crystals with mp 155°-160°. Uv λ sh 213 mμ (ε=36,000) max 266 (20,500) ir (CHCl3) 1715 cm-1 (COOCH3); nmr (CDCl3) δ 3.93 ppm (s, 3, COOCH3) 4.23 (s, 3, OCH3) 4.08 (d, 1) and 6.06 (d, 1) AB-system, J=12 Hz, C4 --H) 7.1-7.9 (m, 7, aromatic H).

Workup

  1. customThe solvent was removed at reduced pressure
  2. dissolutionThe residue was dissolved in methylene chloride
  3. washwashed with dilute hydrochloric acid
  4. customto give pale yellow amorphous solid
  5. washAn ethereal solution (60 ml) of the solid was washed with dilute ammonium hydroxide solution
  6. customdried
  7. filtrationfiltered
  8. concentrationconcentrated on a steam bath to about 20 ml
  9. customWhite crystals were obtained
  10. customat room temperature
  11. customfor several hours
  12. customRecrystallization from ether
  13. customgave white crystals with mp 155°-160°

Sources & evidence

ORD record
ord-2d9a495a99a34c33b97fb8de1675ad77
Source dataset
uspto-grants-1979_08
Patent number
US04166185

Reaction notes

Loading…