Hydrochloric Acid → 4-Vinylphenol

HRID 1760906Notes

Reaction equation

HRID 1760906 reaction equation
C([O:5][C:6]1[CH:13]=[CH:12][C:9]([CH:10]=[CH2:11])=[CH:8][CH:7]=1)(C)(C)C.[C:14]([O:18][C:19]12[CH2:28][CH:23]3[CH2:24][CH:25]([CH2:27][CH:21]([CH2:22]3)[CH:20]1O)[CH2:26]2)(=[O:17])[CH:15]=[CH2:16].N(C(C)(C)C(OC)=O)=NC(C)(C)C(OC)=[O:34].Cl>CC(O)C.CCCCCCC.CO>[OH:5][C:6]1[CH:13]=[CH:12][C:9]([CH:10]=[CH2:11])=[CH:8][CH:7]=1.[C:14]([O:18][C:19]12[CH2:28][CH:23]3[CH2:24][CH:25]([CH2:27][C:21]([OH:34])([CH2:22]3)[CH2:20]1)[CH2:26]2)(=[O:17])[CH:15]=[CH2:16]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 757631,1'-Dimethyl 2,2'-(1,2-diazenediyl)bis(2-methylpropanoate)HCID 5775311-(Tert-butoxy)-4-ethenylbenzeneHCID 54542510HCID 54542510, compound

Product 2

HCID 624534-VinylphenolHCID 222287903-Hydroxy-1-adamantyl acrylate

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 3776IsopropanolSolvent4×HCID 8900HeptaneSolvent

Conditions

Temperature
75 °C

Procedure

Into a flask was charged 92.8 g (0.53 mol) of 4-tert-butoxystyrene, 13.0 g (0.06 mol) of 3 hydroxy-1-adamantyl acrylate, 52.9 g of methanol and 105.8 g of 2-propanol, and they were refluxed under a nitrogen atmosphere at 75° C. Separately, 6.1 g of dimethyl 2,2′-azobis(2-methylpropionate) was dissolved in 17.6 g of 2-propanol to prepare a solution which was dropped into the above-mentioned monomer solution kept at 75° C. over 30 minutes, then, the resulted mixture was refluxed itself for 8 hours. To this was further added 193.9 g of 2-propanol, and the resulted mixture was refluxed again at 75° C. Into this solution was dropped a mixed solution of 18.3 g of 36% hydrochloric acid and 18.3 g of 2-propanol. Subsequently, the mixture was refluxed for 4 hours at the same temperature to cause hydrolysis, then, the solution was cooled to room temperature. To this reaction mass was added 528.9 g of n-heptane, and the lower resin layer was removed. This resin layer was dissolved in 52.9 g of acetone, and 528.9 g of n-heptane was added, and the lower resin layer was removed again. The resulted resin layer was dissolved in 634.7 g of methyl isobutyl ketone, and 211.6 g of ion exchanged water was added to this and the mixture was stirred and allowed to stand still, then, the organic layer part was removed. Further, an operation of addition of 211.6 g of ion exchanged water, stirring and separation was repeated four times. This organic layer was distilled under reduced pressure until the solution amount after distillation was 230.8 g under conditions of a temperature of 60° C. and a pressure of 80 Torr or less, and dehydrated azeotropically, to obtain a methyl isobutyl ketone solution of a copolymer of 4-hydroxystyrene and 3-hydroxy-1-adamantyl acrylate. The solid concentration of the resulted resin solution was 26.3%, and this copolymer had a weight-average molecular weight of 11400 and a polydispersity of 1.77.

Workup

  1. customto prepare a solution which
  2. additionwas dropped into the above-mentioned monomer solution
  3. temperaturethe resulted mixture was refluxed itself for 8 hours
  4. temperaturethe resulted mixture was refluxed again at 75° C
  5. temperatureSubsequently, the mixture was refluxed for 4 hours at the same temperature
  6. customhydrolysis
  7. temperaturethe solution was cooled to room temperature
  8. customthe lower resin layer was removed
  9. dissolutionThis resin layer was dissolved in 52.9 g of acetone
  10. addition528.9 g of n-heptane was added
  11. customthe lower resin layer was removed again
  12. dissolutionThe resulted resin layer was dissolved in 634.7 g of methyl isobutyl ketone
  13. additionwas added to this and the mixture
  14. customthe organic layer part was removed
  15. additionFurther, an operation of addition of 211.6 g of ion
  16. stirringstirring
  17. customseparation
  18. distillationThis organic layer was distilled under reduced pressure until the solution amount
  19. distillationafter distillation
  20. customunder conditions of a temperature of 60° C.

Sources & evidence

ORD record
ord-3d164a94b8cc4142b4aee7f526505dd8
Source dataset
uspto-grants-2005_01
Patent number
US06846609B2

Reaction notes

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