Thiophenol → 5-Phenylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

HRID 1198367Notes

Reaction equation

HRID 1198367 reaction equation
Cl[C:2]1[CH:25]=[CH:24][C:5]2=[N:6][N:7]([C:9]3[CH:14]=[C:13]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:12]=[C:11]([C:19]([CH3:22])([CH3:21])[CH3:20])[C:10]=3[OH:23])[N:8]=[C:4]2[CH:3]=1.[C:26]1([SH:32])[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.[OH-].[Na+]>CN(C)C=O>[C:26]1([S:32][C:2]2[CH:25]=[CH:24][C:5]3=[N:6][N:7]([C:9]4[CH:14]=[C:13]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:12]=[C:11]([C:19]([CH3:22])([CH3:21])[CH3:20])[C:10]=4[OH:23])[N:8]=[C:4]3[CH:3]=2)[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 14798Sodium HydroxideHCID 774702,4-Di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol

Product 1

HCID 193491505-Phenylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

Into a two-liter three-necked flask equipped with stirrer, thermometer, distillation set-up and nitrogen supply are charged 268.4 g (0.75 mole) of 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 93.7 g (0.825 mole) of thiophenol and 400 mL of N,N-dimethylformamide (DMF). The reactor is evacuated and filled with nitrogen three times to establish an inert atmosphere. To the slurry is added 66.0 g (0.825 mole) of 50% aqueous sodium hydroxide solution and the mixture heated to reflux. At this point water distills off as an azeotrope until the head-temperature reaches 132° C. and a reaction temperature of 150° C. After 18 hours there is no residual starting benzotriazole compound observed (TLC). At reduced pressure most of the DMF is distilled off at 80° C. To the residue is then charged 500 mL of toluene and 200 mL of water. After slow stirring for a few minutes at 80° C. the lower aqueous phase is drained off. The addition of 200 mL of water is repeated twice more, the second time with addition of 1 mL of acetic acid. Any residual water is azeotroped off until a clear solution is obtained. Approximately 300 mL of toluene is removed under partial vacuum at 90° C. and to the concentrate is added 800 mL of isopropanol, resulting in rapid crystallization. The reaction mixture is cooled to 20° C. and filtered. The light yellow crystals are washed with 250 ml of isopropanol and dried to give 317 g (97.9% of theory) of the title compound, mp. 132°-134° C.

Workup

  1. customInto a two-liter three-necked flask equipped with stirrer
  2. distillationthermometer, distillation set-up and nitrogen
  3. customThe reactor is evacuated
  4. additionfilled with nitrogen three times
  5. temperaturethe mixture heated to reflux
  6. distillationAt this point water distills off as an azeotrope until the head-temperature reaches 132° C.
  7. customa reaction temperature of 150° C
  8. distillationAt reduced pressure most of the DMF is distilled off at 80° C
  9. additionTo the residue is then charged 500 mL of toluene and 200 mL of water
  10. additionThe addition of 200 mL of water
  11. additionthe second time with addition of 1 mL of acetic acid
  12. customAny residual water is azeotroped off until a clear solution
  13. customis obtained
  14. customApproximately 300 mL of toluene is removed under partial vacuum at 90° C. and to the concentrate
  15. additionis added 800 mL of isopropanol
  16. customresulting in rapid crystallization
  17. temperatureThe reaction mixture is cooled to 20° C.
  18. filtrationfiltered
  19. washThe light yellow crystals are washed with 250 ml of isopropanol
  20. customdried

Sources & evidence

ORD record
ord-dc781e90e6944c39b0a0c043de4eeee8
Source dataset
uspto-grants-1994_01
Patent number
US05280124

Reaction notes

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