Ammonium Hydroxide → 6,6'-Bis(phenylethynyl)[1,1'-biphenyl]-3,3',4,4'-tetramine

HRID 267841Notes

Reaction equation

HRID 267841 reaction equation
[C:1]1([C:7]#[C:8][C:9]2[CH:14]=[C:13]([NH2:15])[C:12]([N+:16]([O-])=O)=[CH:11][C:10]=2[C:19]2[CH:25]=[C:24]([N+:26]([O-])=O)[C:22]([NH2:23])=[CH:21][C:20]=2[C:29]#[C:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH-].[NH4+]>O1CCOCC1.O>[C:31]1([C:30]#[C:29][C:20]2[CH:21]=[C:22]([NH2:23])[C:24]([NH2:26])=[CH:25][C:19]=2[C:10]2[CH:11]=[C:12]([NH2:16])[C:13]([NH2:15])=[CH:14][C:9]=2[C:8]#[C:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1

Participants

5

Reactant 2

HCID 14923Ammonium Hydroxide2×HCID 21554339HCID 21554339, compound

Product 1

HCID 226252996,6'-Bis(phenylethynyl)[1,1'-biphenyl]-3,3',4,4'-tetramineYield 76%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent2×

Procedure

A solution of 2,2'-bis(phenylethynyl)-5,5'-dinitrobenzidine (0.474 g, 0.00100 mol) in dioxane (50 ml), freshly distilled from FeSO4 (3.65 g, 0.024 mol), was added to a boiling solution of FeSO4 (3.65 g, 0.024 mol) in water (50 ml.) which was stirred under nitrogen. After 5 minutes, ammonium hydroxide (20 ml, 30%) was added slowly followed by 20 ml. more of dioxane. The resultant dark suspension was stirred and refluxed for 30 minutes at which point additional ammonium hydroxide (20 ml) was added. Refluxing was continued for 30 minutes and then the reaction mixture was cooled and extracted three times with 100 ml. of chloroform. The combined chloroform extracts were concentrated to dryness on a rotary evaporator. The residue was dissolved in methylene chloride (20 ml.) and filtered after which the filtrate was poured with stirring into 20 ml. of hexane. The resultant precipitate was filtered, washed with hexane, and dried at 23° C in a vacuum oven at 1 mm of Hg for 24 hours to give 0.313 g (76% yield) of 2,2'-bis(phenylethynyl)-5,5'-diaminobenzidine which softened above 100° C to a viscous melt.

Workup

  1. stirringThe resultant dark suspension was stirred
  2. additionwas added
  3. temperatureRefluxing
  4. waitwas continued for 30 minutes
  5. temperaturethe reaction mixture was cooled
  6. extractionextracted three times with 100 ml
  7. concentrationThe combined chloroform extracts were concentrated to dryness on a rotary evaporator
  8. dissolutionThe residue was dissolved in methylene chloride (20 ml.)
  9. filtrationfiltered after which the filtrate
  10. additionwas poured
  11. stirringwith stirring into 20 ml
  12. filtrationThe resultant precipitate was filtered
  13. washwashed with hexane
  14. customdried at 23° C in a vacuum oven at 1 mm of Hg for 24 hours

Sources & evidence

ORD record
ord-450e3532781e4938a2fc4e14e3d7e875
Source dataset
uspto-grants-1976_03
Patent number
US03944614

Reaction notes

Loading…