Hydrazine hydrate (1:1) → 2,2-Bis[4-(3-aminophenoxy)phenyl]propane

HRID 1461901Notes

Reaction equation

HRID 1461901 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:33]=[CH:34][CH:35]=1)[O:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]([C:17]2[CH:22]=[CH:21][C:20]([O:23][C:24]3[CH:29]=[CH:28][CH:27]=[C:26]([N+:30]([O-])=O)[CH:25]=3)=[CH:19][CH:18]=2)([CH3:16])[CH3:15])=[CH:10][CH:9]=1)([O-])=O.O.NN>COCCO>[NH2:30][C:26]1[CH:25]=[C:24]([CH:29]=[CH:28][CH:27]=1)[O:23][C:20]1[CH:19]=[CH:18][C:17]([C:14]([C:11]2[CH:12]=[CH:13][C:8]([O:7][C:6]3[CH:33]=[CH:34][CH:35]=[C:4]([NH2:1])[CH:5]=3)=[CH:9][CH:10]=2)([CH3:15])[CH3:16])=[CH:22][CH:21]=1

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 22460842,2-Bis[4-(3-nitrophenoxy)phenyl]propane

Product 1

HCID 21798162,2-Bis[4-(3-aminophenoxy)phenyl]propaneYield 75%

Reagents, catalysts & solvents 1

HCID 80192-MethoxyethanolSolvent

Procedure

In the second step, a 500 ml glass reaction vessel was charged with 100 grams (0.21 mol) of 2,2-bis[4-(3-nitrophenoxy)phenyl]propane, 10 grams of active carbon, 1 gram of ferric chloride hexa-hydrate and 300 ml of ethyleneglycol monomethylether. The mixture was refluxed with stirring for 30 minutes, followed by dropping 42 grams (0.84 mol) of hydrazine hydrate at 70°-80° C. during 2 hours, and stirred for further 5 hours at 70°-80° C. The resultant reaction mixture was cooled, filtered to remove the catalyst and 150 ml of ethyleneglycol monomethylether was distilled off. To the residual matter, 270 grams of 20% aqueous hydrogen chloride solution and 30 grams of sodium chloride were added, and cooled to 20°-25° C. with stirring. The separated crystals were filtered, dissolved into 30% aqueous IPA solution and neutralized with aqueous ammonia to separate crystals. The crystals were filtered, washed with water, dried and recrystallized from a mixture of benezene and n-hexane. Colorless crystals of 2,2-bis[4-(3-aminophenoxy)phenyl]propane thus obtained were 69.2 grams (75% yield) and had a melting point of 106°-108° C. and their analytical results were as follows.

Workup

  1. temperatureThe mixture was refluxed
  2. customat 70°-80° C.
  3. customduring 2 hours
  4. stirringstirred for further 5 hours at 70°-80° C
  5. customThe resultant reaction mixture
  6. temperaturewas cooled
  7. filtrationfiltered
  8. customto remove the catalyst and 150 ml of ethyleneglycol monomethylether
  9. distillationwas distilled off
  10. additionTo the residual matter, 270 grams of 20% aqueous hydrogen chloride solution and 30 grams of sodium chloride were added
  11. temperaturecooled to 20°-25° C.
  12. stirringwith stirring
  13. filtrationThe separated crystals were filtered
  14. dissolutiondissolved into 30% aqueous IPA solution
  15. customto separate crystals
  16. filtrationThe crystals were filtered
  17. washwashed with water
  18. customdried
  19. customrecrystallized from a mixture of benezene and n-hexane

Sources & evidence

ORD record
ord-0b06e9b34de541aeb52f2b8b06d14e6b
Source dataset
uspto-grants-1991_12
Patent number
US05077436

Reaction notes

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