Sulfuric Acid → HCID 136353527, compound

HRID 1076203Notes

Reaction equation

HRID 1076203 reaction equation
[CH:1]1[C:11]2[C:10](=S)[NH:9][C:8]3[CH:13]=[CH:14][CH:15]=[CH:16][C:7]=3[NH:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.CO[CH:19](OC)[CH:20]([NH2:22])[CH3:21].S(=O)(=O)(O)O.[OH-].[Na+]>C(O)CCC>[CH3:21][C:20]1[N:22]=[C:10]2[C:11]3[CH:1]=[CH:2][CH:3]=[CH:4][C:5]=3[NH:6][C:7]3[CH:16]=[CH:15][CH:14]=[CH:13][C:8]=3[N:9]2[CH:19]=1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 936582,2-Dimethoxy-1-methylethylamineHCID 303289111H-Dibenzo(b,e)(1,4)diazepine-11-thione, 5,10-dihydro-

Product 1

HCID 136353527HCID 136353527, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 2631-ButanolSolvent2×

Procedure

in a 250-ml., three-neck flask fitted with a condenser, is heated to reflux 6.25 g. of 5,10-dihydro-11H-dibenzo-[b,e][1,4]diazepine-11-thione (30.0 mmol.) and 10.8 g. of aminopropionaldehyde dimethyl acetal (90.0 mmol.) in 60 ml. of n-butanol, during 2 hours. An additional 60 ml. of n-butanol is added and the mixture is refluxed overnight (22 hours). At this point, 60 ml. of n-butanol is distilled from the reaction mixture and refluxing is maintained for an additional 18 hours. On cooling, 2.0 g. of crude starting material is obtained. This is added to the reaction mixture along with an additional 5.4 g. of aminopropionaldehyde acetal (40.0 mmol.) and heating is maintained over a weekend (65 hours). On cooling and removal of the solvent in vacuo, 10 g. of brown oil is obtained. The oil is dissolved in 80 ml. of concentrated sulfuric acid and stirred at room temperature under nitrogen for 10 hours. The reaction mixture is then poured into ice and carefully neutralized with 50% aqueous sodium hydroxide solution. The basic aqueous solution is extracted thoroughly with chloroform. The combined chloroform extracts are washed with brine, dried over anhydrous potassium carbonate and concentrated in vacuo. The resulting oil is taken up in ethyl acetate, treated with activated charcoal and filtered. On concentrating and cooling the filtered solution, 3.2 g. of 2-methyl-9H-dibenzo[b,f]imidazo[1,2-d][1,4]diazepine is obtained in 2 crops (yield 40%) of melting point 232°-236° C.

Workup

  1. custom, three-neck flask fitted with a condenser
  2. temperatureis heated
  3. temperatureto reflux 6.25 g
  4. temperaturethe mixture is refluxed overnight (22 hours)
  5. distillationof n-butanol is distilled from the reaction mixture
  6. temperaturerefluxing
  7. temperatureis maintained for an additional 18 hours
  8. temperatureOn cooling
  9. customis obtained
  10. additionThis is added to the reaction mixture along with an additional 5.4 g
  11. temperatureis maintained over a weekend (65 hours)
  12. temperatureOn cooling
  13. customremoval of the solvent in vacuo, 10 g
  14. customof brown oil is obtained
  15. dissolutionThe oil is dissolved in 80 ml
  16. additionThe reaction mixture is then poured into ice
  17. extractionThe basic aqueous solution is extracted thoroughly with chloroform
  18. washThe combined chloroform extracts are washed with brine
  19. dry with materialdried over anhydrous potassium carbonate
  20. concentrationconcentrated in vacuo
  21. additiontreated with activated charcoal
  22. filtrationfiltered
  23. concentrationOn concentrating
  24. temperaturecooling the filtered solution, 3.2 g

Sources & evidence

ORD record
ord-cac12814970f4b9e96f2f12f17f03f91
Source dataset
uspto-grants-1976_05
Patent number
US03956297

Reaction notes

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