Hydrazine → 1,4-Benzenediamine, N,N'-bis(4-aminophenyl)-

HRID 1275424Notes

Reaction equation

HRID 1275424 reaction equation
C1C=CC([NH:7][C:8]2[CH:13]=[CH:12][C:11]([NH:14][C:15]3[CH:20]=[CH:19][C:18]([NH:21][C:22]4[CH:27]=[CH:26][C:25]([NH2:28])=[CH:24][CH:23]=4)=[CH:17][CH:16]=3)=[CH:10][CH:9]=2)=CC=1.NN>C(O)C>[CH:13]1[C:8]([NH2:7])=[CH:9][CH:10]=[C:11]([NH:14][C:15]2[CH:20]=[CH:19][C:18]([NH:21][C:22]3[CH:27]=[CH:26][C:25]([NH2:28])=[CH:24][CH:23]=3)=[CH:17][CH:16]=2)[CH:12]=1

Participants

4

Reactant 2

HCID 9321HydrazineHCID 110685681,4-Benzenediamine, N-(4-aminophenyl)-N'-[4-(phenylamino)phenyl]-

Product 1

HCID 110007731,4-Benzenediamine, N,N'-bis(4-aminophenyl)-

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

About 5.0 g of the tetraaniline in the emeraldine oxidation state synthesized in Example 2 was dissolved in 250 ml ethanol. 10 ml of anhydrous hydrazine was added with constant magnetic stirring. The reaction system was stirred for about 2 hours. The blue precipitate was collected by vacuum filtration and washed with 100 ml cold ethanol in 3 portions. The precipitate was suspended in 700 ml ethanol containing 1 ml of phenylhydrazine which was heated to reflux for 0.5 hours. The heat was removed and about 2.5 g of active carbon was added. The suspension was heated to reflux for another 0.5 hours and then was filtered hot by vacuum filtration and the filtrate was cooled in an ice bath. The off white precipitate was collected by vacuum filtration and washed with 50 ml cold ethanol and dried under dynamic vacuum. This precipitate was readily oxidized to, or approaching, the emeraldine oxidation state by air, especially if wet or in solution. Hence, minimum exposure to air is necessary in order to obtain the tetramer in the leucoemeraldine oxidation state. The dried precipitate was ground and stored in a dark bottle under Argon in a refrigerator. The yield was 3.5 g or 70%. A typical analysis for the tetraaniline in the leucoemeraldine oxidation state C24H22N4 was C: 78.38; H: 6.02; N: 15.28, total 99.68%. Calculated, C: 78.68; H: 6.05; N: 15.29. Mass spectrum (CI): 367 (MH+ /e). 1H NMR (DMSO): 7.66 (s,1), 7.42 (s,1), 7.15 (s,1), 7.12 (t,2), 6.88 (m,12), 6.65 (t,1), 6.52 (d,2) and 4.63 (s,2). 13C NMR (DMSO): 145.7, 142.6, 139.9, 139.8. 135.1, 134.1, 133.5, 129.0, 121.0, 120.5, 119.6, 117.7, 116.3, 115.9, 114.9 and 114.4 (TMS std.). These data are in agreement with the proposed structure, and are presented in FIG. 3 where it is identified as "B."

Workup

  1. filtrationThe blue precipitate was collected by vacuum filtration
  2. washwashed with 100 ml cold ethanol in 3 portions
  3. temperaturewas heated
  4. temperatureto reflux for 0.5 hours
  5. customThe heat was removed
  6. additionabout 2.5 g of active carbon was added
  7. temperatureThe suspension was heated
  8. temperatureto reflux for another 0.5 hours
  9. filtrationwas filtered hot by vacuum filtration
  10. temperaturethe filtrate was cooled in an ice bath
  11. filtrationThe off white precipitate was collected by vacuum filtration
  12. washwashed with 50 ml cold ethanol
  13. customdried under dynamic vacuum

Sources & evidence

ORD record
ord-576c10e79bab4c4680c5f65aeb3b3139
Source dataset
uspto-grants-2000_12
Patent number
US06160177

Reaction notes

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