Sodium Iodide → 3,3'-[[1,1'-Biphenyl]-4,4'-diylbis(phenylazanediyl)]diphenol

HRID 355302Notes

Reaction equation

HRID 355302 reaction equation
C[O:2][C:3]1[CH:4]=[C:5]([N:9]([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C:10]2[CH:15]=[CH:14][C:13]([C:16]3[CH:21]=[CH:20][C:19]([N:22]([C:29]4[CH:34]=[CH:33][CH:32]=[C:31]([O:35]C)[CH:30]=4)[C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)=[CH:18][CH:17]=3)=[CH:12][CH:11]=2)[CH:6]=[CH:7][CH:8]=1.[I-].[Na+].S1(CCCC1)(=O)=O.C[Si](C)(C)Cl>CC(C)=O.CCCCCCC.O>[C:37]1([N:9]([C:5]2[CH:6]=[CH:7][CH:8]=[C:3]([OH:2])[CH:4]=2)[C:10]2[CH:11]=[CH:12][C:13]([C:16]3[CH:17]=[CH:18][C:19]([N:22]([C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)[C:29]4[CH:34]=[CH:33][CH:32]=[C:31]([OH:35])[CH:30]=4)=[CH:20][CH:21]=3)=[CH:14][CH:15]=2)[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1

Participants

8

Reactant 4

HCID 5238Sodium IodideHCID 6397ChlorotrimethylsilaneHCID 31347SulfolaneHCID 10768984HCID 10768984, compound2×

Product 1

HCID 143890713,3'-[[1,1'-Biphenyl]-4,4'-diylbis(phenylazanediyl)]diphenolYield 85%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolvent2×HCID 8900HeptaneSolvent

Conditions

Temperature
120 °C

Procedure

N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-(1,1'-biphenyl)-4,4'-diamine was prepared, for example, from N,N'-di(3-methoxyphenyl)-N,N'-diphenyl-[1,1'-biphenyl]-4,4'diamine by placing into a two liter three-necked round bottom flask, equipped with a mechanical stirrer and an argon gas inlet, 137.5 gms, N,N'-diphenyl-N,N'-bis(3-methoxy phenyl)-[1,1'-biphenyl]-4,4'diamine (0.25 moles), 223.5 gms anhydrous sodium iodide (1.5 moles) and 500 milliliters warm sulfolane (distilled). The contents of the flask were heated to 120° C. and then cooled to 60° C. Five milliliters of D.I. water was added dropwise, followed by 190.5 milliliters of trimethyl(chlorosilane) (1.5 moles). The contents were allowed to reflux for six hours. HPLC analysis was utilized to determine when the reaction was complete. The contents of the flask were poured into a 3 liter Erlenmeyer flask containing 1.5 liter of deionized water. The water layer was decanted and the dark oily residue taken up into 500 milliliters methanol. The methanol solution was extracted with two 400 milliliter portions of hexane to remove the hexamethyldisiloxane by-products. The methanol solution was roto-evaporated to remove the solvents. The residue was taken up in 500 milliliters of acetone and then precipitated into 1.5 liters deionized water. The off-white solid was filtered and then washed with deionized water and dried in vacuo. The crude N,N'diphenyl-N,N'-bis(3-hydroxyphenyl)-(1,1'-biphenyl)-4,4'-diamine was placed into a two liter round-bottom flask containing a magnetic stirrer and one liter toluene. Fifty gms. of Florisil® (Florisil is a registered trademark of Floridin Co.) was added to the flask and allowed to stir for two hours. The dark Florisil® was filtered off, leaving a pale yellow toluene solution. The toluene was roto-evaporated to yield a pale yellow viscous oil. The oily product was dissolved in 400 milliliters acetone, then diluted with 400 milliliters heptane and allowed to crystallize. The colorless crystals were filtered. Additional product was obtained by roto-evaporating the acetone from the filtrate. Yield was 85 percent, m.p. 113°-17° C.

Workup

  1. customby placing into a two liter three-necked round bottom flask
  2. customequipped with a mechanical stirrer and an argon gas inlet
  3. temperaturecooled to 60° C
  4. temperatureto reflux for six hours
  5. additionThe contents of the flask were poured into a 3 liter Erlenmeyer flask
  6. customThe water layer was decanted
  7. extractionThe methanol solution was extracted with two 400 milliliter portions of hexane
  8. customto remove the hexamethyldisiloxane by-products
  9. customThe methanol solution was roto-evaporated
  10. customto remove the solvents
  11. customprecipitated into 1.5 liters
  12. filtrationThe off-white solid was filtered
  13. washwashed with deionized water
  14. customdried in vacuo
  15. customThe crude N,N'diphenyl-N,N'-bis(3-hydroxyphenyl)-(1,1'-biphenyl)-4,4'-diamine was placed into a two liter round-bottom flask
  16. additioncontaining a magnetic stirrer
  17. addition) was added to the flask
  18. filtrationThe dark Florisil® was filtered off
  19. customleaving a pale yellow toluene solution
  20. customThe toluene was roto-evaporated
  21. customto yield a pale yellow viscous oil
  22. customto crystallize
  23. filtrationThe colorless crystals were filtered
  24. customAdditional product was obtained
  25. customby roto-evaporating the acetone from the filtrate

Sources & evidence

ORD record
ord-87425a5724bc4aea9d8fa5f633916780
Source dataset
uspto-grants-1998_11
Patent number
US05830614

Reaction notes

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