Aniline → N,N,N'-triphenyl-4-phenylenediamine

HRID 634535Notes

Reaction equation

HRID 634535 reaction equation
[CH:1]1[CH:6]=[CH:5][C:4]([N:7]([C:14]2[CH:19]=[CH:18][C:17](Br)=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:3][CH:2]=1.CC(C)([O-])C.[Na+].[NH2:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.CCCCCC.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].C1(C)C=CC=CC=1>[C:4]1([N:7]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:14]2[CH:19]=[CH:18][C:17]([NH:27][C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)=[CH:16][CH:15]=2)[CH:5]=[CH:6][CH:1]=[CH:2][CH:3]=1

Participants

8

Reactant 5

HCID 6115AnilineHCID 8058HexaneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 6428384-BromotriphenylamineHCID 23676156Sodium t-butoxide

Product 1

HCID 161288N,N,N'-triphenyl-4-phenylenediamineYield 42%

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

0.56 g (6 mmol) of 4-bromotriphenylamine, 0.35 g (0.6 mmol) of bis(dibenzylideneacetone)palladium(0), and 0.58 g (6 mmol) of sodium-tert-butoxide were put into a 100 mL three neck flask, and 5 mL of toluene was added thereto. After nitrogen was substituted for the content of the flask, 0.56 g (6 mmol) of aniline and 0.37 mL (1.8 mmol) of a hexane solution (10 wt %) of tri-tert-butylphosphine were added. This mixture was stirred for 5 hours at 80° C. to be reacted. After the reaction, the reaction was completed by adding a saturated saline solution to the reaction mixture, and an aqueous layer was extracted by approximately 100 mL of ethyl acetate to be separated from an organic layer. The organic layer was dried with magnesium sulfate and filtered. A solid that was obtained by concentrating the filtrate was purified by silica column chromatography, whereby 0.24 g of a light yellow powder solid of DPA that is an object was obtained in the yield of 42% (Synthesis Scheme (i-2)). For the column purification, a mixed solvent of ethyl acetate:hexane=1:20 was used as a developing solvent.

Workup

  1. additionwas added
  2. additionwere added
  3. customto be reacted
  4. customAfter the reaction
  5. additionby adding a saturated saline solution to the reaction mixture
  6. extractionan aqueous layer was extracted by approximately 100 mL of ethyl acetate
  7. customto be separated from an organic layer
  8. dry with materialThe organic layer was dried with magnesium sulfate
  9. filtrationfiltered
  10. customA solid that was obtained
  11. concentrationby concentrating the filtrate
  12. customwas purified by silica column chromatography, whereby 0.24 g of a light yellow powder solid of DPA that
  13. customwas obtained in the yield of 42% (Synthesis Scheme (i-2))
  14. customFor the column purification

Sources & evidence

ORD record
ord-1691873a788845f5b96f46aaca1dabf3
Source dataset
uspto-grants-2016_04
Patent number
US09324951B2

Reaction notes

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