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

HRID 1086299Notes

Reaction equation

HRID 1086299 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.O>CC(C)=O.CCCCCCC.C1(C)C=CC=CC=1>[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 962Water2×HCID 5238Sodium IodideHCID 31347SulfolaneHCID 10768984HCID 10768984, compound2×

Product 1

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

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 1140TolueneSolventHCID 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 the 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 anhydrons sodium iodide (1.5 moles) and 500 millileters warm sulfolane (distilled). The contents of the flask were heated to 120° C. then cooled to 60° C. Five millileters of D.I. water was added dropwise, followed by 190.5 millileters 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-evaported to remove the solvents. The residue was taken up into 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. 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 yelow toluene solution. The toluene was rotoevaporated 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. temperaturethen cooled 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. customto remove the solvents
  10. customprecipitated into 1.5 liters
  11. filtrationThe off-white solid was filtered
  12. washwashed with deionized water
  13. customdried in vacuo
  14. 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
  15. additioncontaining a magnetic stirrer
  16. addition) was added to the flask
  17. filtrationThe dark Florisil® was filtered off
  18. customleaving a pale yelow toluene solution
  19. customto yield a pale yellow viscous oil
  20. customto crystallize
  21. filtrationThe colorless crystals were filtered
  22. customAdditional product was obtained
  23. customby roto-evaporating the acetone from the filtrate

Sources & evidence

ORD record
ord-4b23559586b54132898c0be2c8533b64
Source dataset
uspto-grants-1991_07
Patent number
US05028687

Reaction notes

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