Sodium Iodide → HCID 10768984, compound

HRID 2350840Notes

Reaction equation

HRID 2350840 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

Following 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-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. then cooled to 60° C. Five milliliters of D.I. water was added dropwise, followed by 190.5 milliliters of trimethylchlorosilane (1.5 moles)). The contents were allowed to heat at 60°-75° C. 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 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. temperaturethen cooled to 60° C
  4. temperatureto heat at 60°-75° C. 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 yellow toluene solution
  19. customThe toluene was roto-evaporated
  20. customto yield a pale yellow viscous oil
  21. customto crystallize
  22. filtrationThe colorless crystals were filtered
  23. customAdditional product was obtained
  24. customby roto-evaporating the acetone from the filtrate

Sources & evidence

ORD record
ord-ae0a4016d11d4d36b77deb1837fa721c
Source dataset
uspto-grants-1989_10
Patent number
US04871634

Reaction notes

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