Hydrazine hydrate (1:1) → HCID 1820695, compound

HRID 1461902Notes

Reaction equation

HRID 1461902 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:39]=[CH:40][CH:41]=1)[O:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]([C:23]2[CH:28]=[CH:27][C:26]([O:29][C:30]3[CH:35]=[CH:34][CH:33]=[C:32]([N+:36]([O-])=O)[CH:31]=3)=[CH:25][CH:24]=2)([C:19]([F:22])([F:21])[F:20])[C:15]([F:18])([F:17])[F:16])=[CH:10][CH:9]=1)([O-])=O.O.NN>CC(O)C>[NH2:1][C:4]1[CH:5]=[C:6]([CH:39]=[CH:40][CH:41]=1)[O:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]([C:23]2[CH:28]=[CH:27][C:26]([O:29][C:30]3[CH:35]=[CH:34][CH:33]=[C:32]([NH2:36])[CH:31]=3)=[CH:25][CH:24]=2)([C:19]([F:20])([F:21])[F:22])[C:15]([F:18])([F:17])[F:16])=[CH:10][CH:9]=1

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 19979709HCID 19979709, compound

Product 1

HCID 1820695HCID 1820695, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Conditions

Temperature
22.5 °C

Procedure

In the next step, a 300 ml glass reaction vessel was charged with 20 grams (0.035 mol) of crude 2,2-bis[4-(3-nitrophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2 grams of active carbon, 0.2 gram of ferric chloride hexahydrate and 100 ml of IPA. The mixture was refluxed for 30 minutes with stirring and 7 grams (0.14 mol) of hydrazine hydrate was dropwise added at 60-70° C. during 2 hours, and refluxed for further 5 hours with stirring. The resultant reaction mixture was cooled, filtered to remove the catalyst and heated to distill off 60 ml of IPA. To the residue, 80 grams of 17.5% aqueous hydrochloric acid and 10 grams of sodium chloride were added and cooled to 20-25° C. with stirring. The separated crystals were filtered and recrystallized again from 40 ml of IPA and 80 grams of 17.5% aqueous hydrochloric acid. The resulting crystals were dissolved into 50% aqueous IPA solution and neutralized with aqueous ammonia to separate crystals. The crystals were filtered, washed with water, dried and recrystallized from the solvent mixture of benzene and n-hexane. Colorless crystals of 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane thus obtained were 13.6 grams (75% yield) and had a melting point of 137-139° C. The analytical results were as follows.

Workup

  1. temperatureThe mixture was refluxed for 30 minutes
  2. temperaturerefluxed for further 5 hours
  3. stirringwith stirring
  4. customThe resultant reaction mixture
  5. temperaturewas cooled
  6. filtrationfiltered
  7. customto remove the catalyst
  8. temperatureheated
  9. distillationto distill off 60 ml of IPA
  10. additionTo the residue, 80 grams of 17.5% aqueous hydrochloric acid and 10 grams of sodium chloride were added
  11. stirringwith stirring
  12. filtrationThe separated crystals were filtered
  13. customrecrystallized again from 40 ml of IPA and 80 grams of 17.5% aqueous hydrochloric acid
  14. dissolutionThe resulting crystals were dissolved into 50% aqueous IPA solution
  15. customto separate crystals
  16. filtrationThe crystals were filtered
  17. washwashed with water
  18. customdried
  19. customrecrystallized from the solvent mixture of benzene and n-hexane

Sources & evidence

ORD record
ord-4524e28d513a442488d2f3906e4c2d70
Source dataset
uspto-grants-1991_12
Patent number
US05077436

Reaction notes

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