Sulfuric Acid → 6-tert-Butylquinoline

HRID 1706440Notes

Reaction equation

HRID 1706440 reaction equation
[CH3:1][C:2]([C:5]1[CH:11]=[CH:10][C:8]([NH2:9])=[CH:7][CH:6]=1)([CH3:4])[CH3:3].S(=O)(=O)(O)O.[N+]([C:20]1[CH:21]=C(S([O-])(=O)=O)C=C[CH:25]=1)([O-])=O.[Na+].[OH-].[Na+]>OCC(CO)O>[CH3:4][C:2]([C:5]1[CH:11]=[C:10]2[C:8](=[CH:7][CH:6]=1)[N:9]=[CH:21][CH:20]=[CH:25]2)([CH3:1])[CH3:3]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 31389Sodium 3-nitrobenzenesulfonateHCID 698614-Tert-Butylaniline

Product 1

HCID 1096386-tert-Butylquinoline

Reagents, catalysts & solvents 1

HCID 753GlycerolSolvent

Procedure

4-(1,1-Dimethylethyl)aniline (185 g.) is added dropwise, with stirring, to 500 ml. of 75% sulfuric acid, followed by 376 g. of sodium 3-nitrobenzenesulfonate in one portion, then 212 g. of glycerol over a 10 minute period. The mixture is stirred for 10 minutes, heated slowly to reflux temperature over a 2.5 hour period, then stirred and heated at reflux for 9 hours. The mixture is cooled, diluted with 400 ml. of ice water, basified with 855 ml. of 50% aqueous sodium hydroxide and warmed to 70° C. The supernatant solution is decanted and extracted with toluene. The toluene extract is in turn extracted with three 800 ml. portions of 2 N hydrochloric acid. The combined acid extract is basified with excess 50% aqueous sodium hydroxide and extracted with toluene. The toluene extract is evaporated at reduced pressure to give a residue of 6-(1,1-dimethylethyl)quinoline which is purified by distillation; b.p. 90°-94° C./ 0.18 mm.

Workup

  1. stirringThe mixture is stirred for 10 minutes
  2. temperatureheated slowly
  3. temperatureto reflux temperature over a 2.5 hour period
  4. stirringstirred
  5. temperatureheated
  6. temperatureat reflux for 9 hours
  7. temperatureThe mixture is cooled
  8. additiondiluted with 400 ml
  9. customThe supernatant solution is decanted
  10. extractionextracted with toluene
  11. extractionThe toluene extract
  12. extractionextracted with three 800 ml
  13. extractionThe combined acid extract
  14. extractionextracted with toluene
  15. extractionThe toluene extract
  16. customis evaporated at reduced pressure

Sources & evidence

ORD record
ord-532925e4692e45c6bec1cc841e4bf94c
Source dataset
uspto-grants-1980_06
Patent number
US04207320

Reaction notes

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