Diethyl Ether → 3-(m-Phenoxyphenoxy)-3'-(p-phenoxyphenoxy)biphenyl

HRID 1076464Notes

Reaction equation

HRID 1076464 reaction equation
[O:1]([C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[K+].Cl[C:18]1[CH:19]=[C:20]([C:24]2[CH:29]=[CH:28][CH:27]=[C:26]([O:30][C:31]3[CH:36]=[CH:35][CH:34]=[C:33]([O:37][C:38]4[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=4)[CH:32]=3)[CH:25]=2)[CH:21]=[CH:22][CH:23]=1.CCOCC>COCCOCCOC>[O:37]([C:33]1[CH:32]=[C:31]([CH:36]=[CH:35][CH:34]=1)[O:30][C:26]1[CH:25]=[C:24]([C:20]2[CH:21]=[CH:22][CH:23]=[C:18]([O:14][C:11]3[CH:10]=[CH:9][C:8]([O:1][C:2]4[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=4)=[CH:13][CH:12]=3)[CH:19]=2)[CH:29]=[CH:28][CH:27]=1)[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 132544-PhenoxyphenolHCID 14797Potassium HydroxideHCID 215369223-Chloro-3'-(m-phenoxyphenoxy)biphenyl

Product 1

HCID 215369233-(m-Phenoxyphenoxy)-3'-(p-phenoxyphenoxy)biphenyl

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent

Conditions

Temperature
150 °C

Procedure

A 250 ml. reaction flask equipped with stirrer, dropping funnel, thermometer, and Dean-Stark trap surmounted by a Friedrichs condenser, was charged with 200 g. (1.07 moles) of p-phenoxyphenol, and 34.9 g. (0.567 mole) of potassium hydroxide was added in increments at 90°C. To the resulting melt was added 50 ml. of toluene and the theoretical amount of water azeotroped from the reaction mixture followed by removal of toluene up to 230°C. On cooling to 150°C., the reaction mixture was diluted with 150 ml. of diglyme and 5.0 g. of cuprous chloride and 1.0 g. of copper powder was added. Over a 45 min. period, 20 g. (0.054 mole) of 3-chloro-3'-(m-phenoxyphenoxy)-biphenyl in diglyme was added, and the diglyme was removed by distillation. The stirred reaction mixture was heated at 235°C. for 19 hours. On cooling, an equal volume of ether was added and this mixture centrifuged to remove salts. The ethereal solution was washed with 25 % potassium hydroxide solution to remove excess phenol, water until neutral, and then dried over anhydrous magnesium sulfate. After filtration and concentration to remove ether, the oil obtained was distilled to obtain 17.5 g. of the desired product, bp 297°-302° C./0.05 mm.; nD25 1.6500.

Workup

  1. customreaction flask
  2. customequipped with stirrer
  3. additionwas charged with 200 g
  4. additionTo the resulting melt was added 50 ml
  5. customof toluene and the theoretical amount of water azeotroped from the reaction mixture
  6. customfollowed by removal of toluene up to 230°C
  7. additionthe reaction mixture was diluted with 150 ml
  8. additionof copper powder was added
  9. customthe diglyme was removed by distillation
  10. customThe stirred reaction mixture
  11. temperaturewas heated at 235°C. for 19 hours
  12. temperatureOn cooling
  13. customto remove salts
  14. washThe ethereal solution was washed with 25 % potassium hydroxide solution
  15. customto remove excess phenol, water until neutral, and
  16. dry with materialthen dried over anhydrous magnesium sulfate
  17. filtrationAfter filtration and concentration
  18. customto remove ether
  19. customthe oil obtained
  20. distillationwas distilled
  21. customto obtain 17.5 g

Sources & evidence

ORD record
ord-9eb6ba4961d54534b5c42e3d3e4df1ab
Source dataset
uspto-grants-1976_05
Patent number
US03957666

Reaction notes

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