Hydroquinone → p-(tetrahydro-4H-1,4-thiazin-4-yl)phenol

HRID 2413976Notes

Reaction equation

HRID 2413976 reaction equation
[C:1]1([CH:8]=[CH:7][C:5]([OH:6])=[CH:4][CH:3]=1)O.[NH:9]1[CH2:14][CH2:13][S:12][CH2:11][CH2:10]1>[Cu]Cl>[S:12]1[CH2:13][CH2:14][N:9]([C:1]2[CH:8]=[CH:7][C:5]([OH:6])=[CH:4][CH:3]=2)[CH2:10][CH2:11]1

Participants

4

Reactant 2

HCID 785HydroquinoneHCID 67164Thiomorpholine

Product 1

HCID 19995894p-(tetrahydro-4H-1,4-thiazin-4-yl)phenol

Reagents, catalysts & solvents 1

HCID 62652Cuprous chlorideCatalyst

Procedure

(aa) A mixture of 99 g of hydroquinone, 13.5 g of copper(I) chloride and 180 ml of thiomorpholine is heated to boiling under reflux under argon for 47 hours. After cooling, the mixture is partitioned between 1N sodium hydroxide solution and dichloromethane, the sodium hydroxide extract is adjusted to about pH 1 with concentrated hydrochloric acid while cooling with ice and then partitioned between 0.1N hydrochloric acid and dichloromethane which contains 10% alcohol. The acidic extracts are adjusted to about pH 6 with 50 percent sodium hydroxide solution while cooling with ice and thereafter extracted in each case three times with dichloromethane which contains 10% alcohol as well as dichloromethane which contains 20% alcohol. The material obtained is distilled in a bulb-tube at 180° and 0.01 Torr and then recrystallized from methanol/ether. p-(Tetra-hydro-4H-1,4-thiazin-4-yl)phenol of melting point 156°-158° is obtained.

Workup

  1. temperatureis heated
  2. temperatureunder reflux under argon for 47 hours
  3. temperatureAfter cooling
  4. customthe mixture is partitioned between 1N sodium hydroxide solution and dichloromethane
  5. extractionthe sodium hydroxide extract
  6. temperaturewhile cooling with ice
  7. custompartitioned between 0.1N hydrochloric acid and dichloromethane which
  8. temperaturewhile cooling with ice
  9. extractionextracted in each case three times with dichloromethane which
  10. customThe material obtained
  11. distillationis distilled in a bulb-tube at 180°
  12. custom0.01 Torr and then recrystallized from methanol/ether

Sources & evidence

ORD record
ord-090cbba5065345289999a2350536f80b
Source dataset
uspto-grants-1988_01
Patent number
US04720546

Reaction notes

Loading…