Sodium Iodide → HCID 10768984, compound

HRID 1382178Notes

Reaction equation

HRID 1382178 reaction equation
IC1C=C(OC)C=CC=1.[CH3:10][O:11][C:12]1[CH:13]=[C:14]([N:18]([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C:19]2[CH:24]=[CH:23][C:22]([C:25]3[CH:30]=[CH:29][C:28]([N:31]([C:38]4[CH:43]=[CH:42][CH:41]=[C:40]([O:44][CH3:45])[CH:39]=4)[C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)=[CH:27][CH:26]=3)=[CH:21][CH:20]=2)[CH:15]=[CH:16][CH:17]=1.[I-].[Na+].S1(CCCC1)(=O)=O.C[Si](C)(C)Cl>CC(C)=O.CCCCCCC.O>[CH3:45][O:44][C:40]1[CH:39]=[C:38]([N:31]([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:28]2[CH:27]=[CH:26][C:25]([C:22]3[CH:23]=[CH:24][C:19]([N:18]([C:14]4[CH:15]=[CH:16][CH:17]=[C:12]([O:11][CH3:10])[CH:13]=4)[C:46]4[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=4)=[CH:20][CH:21]=3)=[CH:30][CH:29]=2)[CH:43]=[CH:42][CH:41]=1.[C:46]1([N:18]([C:14]2[CH:15]=[CH:16][CH:17]=[C:12]([OH:11])[CH:13]=2)[C:19]2[CH:20]=[CH:21][C:22]([C:25]3[CH:26]=[CH:27][C:28]([N:31]([C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)[C:38]4[CH:43]=[CH:42][CH:41]=[C:40]([OH:44])[CH:39]=4)=[CH:29][CH:30]=3)=[CH:23][CH:24]=2)[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1

Participants

10

Reactant 5

HCID 5238Sodium IodideHCID 6397ChlorotrimethylsilaneHCID 31347SulfolaneHCID 69839Benzene, 1-iodo-3-methoxy-HCID 10768984HCID 10768984, compound2×

Product 2

HCID 10768984HCID 10768984, compoundYield 90%HCID 143890713,3'-[[1,1'-Biphenyl]-4,4'-diylbis(phenylazanediyl)]diphenol

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolvent2×HCID 8900HeptaneSolvent

Conditions

Temperature
120 °C

Procedure

Compounds represented by the above hydroxy arylamine formula may be prepared by hydrolyzing an alkoxy arylamine. A typical process for preparing alkoxy arylamines is disclosed in Example I of U.S. Pat. No. 4,588,666 to Stolka et al, the entire disclosure of this patent being incorporated herein by reference. In accordance with the procedure of Example I in U.S. Pat. No. 4,588,666, N,N'-di(3-methoxyphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4' diamine was synthesized from m-iodoanisole to achieve a yield of 90 percent, m.p. 120°-125° C. 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-methoxyphenyl)-[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 milliliters of trimethylchlorosilane (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 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 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 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. Typical compounds represented by the above formula for hydroxy arylamine compounds include: ##STR8## and the like.

Workup

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

Sources & evidence

ORD record
ord-d97776412ad8453a9126ee41c0ac76de
Source dataset
uspto-grants-1989_02
Patent number
US04806444

Reaction notes

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