Toluene → HCID 13008312, compound

HRID 1018722Notes

Reaction equation

HRID 1018722 reaction equation
[C:1]([C:6]1[CH:11]=[CH:10][C:9]([OH:12])=[CH:8][CH:7]=1)([CH2:4][CH3:5])([CH3:3])[CH3:2].[C:13]1([CH3:19])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[NH2:20][C:21]1[CH:26]=[C:25](Cl)[C:24]([N+:28]([O-:30])=[O:29])=[CH:23][C:22]=1[OH:31].[OH-].[K+]>CN(C)C(=O)C>[CH2:19]([O:31][C:22]1[CH:23]=[C:24]([N+:28]([O-:30])=[O:29])[C:25]([O:12][C:9]2[CH:8]=[CH:7][C:6]([C:1]([CH2:4][CH3:5])([CH3:2])[CH3:3])=[CH:11][CH:10]=2)=[CH:26][C:21]=1[NH2:20])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 66434-tert-PentylphenolHCID 14797Potassium HydroxideHCID 38948482-Amino-4-chloro-5-nitrophenol

Product 1

HCID 13008312HCID 13008312, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Conditions

Temperature
90 °C

Procedure

In a 500-ml flask, place 32.0 g (0.15 m×1.3) of 4-t-pentylphenol, 250 ml of toluene, 15 ml of N,N-dimethylacetamide, and 1 1.22 g (0.15 m×1.2@90%) of KOH flakes. Heat the mixture under reflux with Dean-Stark trap to collect approximately 5 ml of water and 20 ml of toluene over 1 hr. Cool white slurry mixture to 90° C., and add 41.8 g (0.15 m) of 2-benzyloxy-5-chloro-4-nitroaniline (2) and 1 g of tetrabutylammonium bromide. Heat under reflux for 1 hr. Addition of 1 g of phase transfer agent, tetrabutylammonium bromide, and heat under reflux for 1 hr period is repeated 3 more times. At the end of the 4 hrs reflux period, cool the reaction mixture to 90° C., add 100 ml of hot water and stir for a few min. Separate toluene solution, wash with 100 ml of hot water, concentrate the reaction mixture by distilling off toluene under a reduced pressure at a pot temperature of 60° C. Add 200 ml of heptane slowly at 60° C., cool to room temperature, and let it stand over night. Collect solid, wash with 10% toluene in heptane, dry in air to give 55.5 g (91%) of 2-benzyloxy-5-(4-t-pentylphenoxy)-4-nitro-aniline (3b; Y=4-t-pentylphenoxy).

Workup

  1. temperatureHeat the mixture
  2. temperatureunder reflux with Dean-Stark trap
  3. customto collect approximately 5 ml of water and 20 ml of toluene over 1 hr
  4. additionadd 41.8 g (0.15 m) of 2-benzyloxy-5-chloro-4-nitroaniline (2) and 1 g of tetrabutylammonium bromide
  5. temperatureHeat
  6. temperatureunder reflux for 1 hr
  7. additionAddition of 1 g of phase transfer agent, tetrabutylammonium bromide
  8. temperatureheat
  9. temperatureunder reflux for 1 hr period
  10. temperatureAt the end of the 4 hrs reflux period
  11. temperaturecool the reaction mixture to 90° C.
  12. additionadd 100 ml of hot water
  13. washSeparate toluene solution, wash with 100 ml of hot water
  14. concentrationconcentrate the reaction mixture
  15. distillationby distilling off toluene under a reduced pressure at a pot temperature of 60° C
  16. additionAdd 200 ml of heptane slowly at 60° C.
  17. temperaturecool to room temperature
  18. waitstand over night
  19. customCollect solid
  20. washwash with 10% toluene in heptane
  21. customdry in air

Sources & evidence

ORD record
ord-671620ffdc4142bda47bb5ae05b86a80
Source dataset
uspto-grants-2002_11
Patent number
US06482953B1

Reaction notes

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