Hydrazine hydrate (1:1) → HCID 21288462, compound

HRID 868407Notes

Reaction equation

HRID 868407 reaction equation
[F:1][C:2]([F:56])([CH2:29][CH2:30][N:31]([S:46]([C:49]1[CH:54]=[CH:53][C:52]([CH3:55])=[CH:51][CH:50]=1)(=[O:48])=[O:47])[CH2:32][CH2:33][CH2:34][N:35]1C(=O)C2=CC=CC=C2C1=O)[CH2:3][N:4]([S:19]([C:22]1[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][CH:23]=1)(=[O:21])=[O:20])[CH2:5][CH2:6][CH2:7][N:8]1C(=O)C2=CC=CC=C2C1=O.O.NN>C(O)C.O.CO.Cl>[NH2:8][CH2:7][CH2:6][CH2:5][N:4]([S:19]([C:22]1[CH:23]=[CH:24][C:25]([CH3:28])=[CH:26][CH:27]=1)(=[O:21])=[O:20])[CH2:3][C:2]([F:56])([F:1])[CH2:29][CH2:30][N:31]([S:46]([C:49]1[CH:54]=[CH:53][C:52]([CH3:55])=[CH:51][CH:50]=1)(=[O:47])=[O:48])[CH2:32][CH2:33][CH2:34][NH2:35]

Participants

7

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 21288463HCID 21288463, compound

Product 1

HCID 21288462HCID 21288462, compound

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent2×HCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 6,6-difluoro-1,12-diphthalimido-4,9-di-p-toluenesulfonyl-4,9-diaza-dodecane (3.4 g, 4.22 mM), ethanol (8.5 mL) and 8.5 mL of a 1N solution of hydrazine hydrate in ethanol is stirred and heated (bath temperature: 90° C.) overnight. Evaporation and stripping twice with methanol yields a residue which is dissolved in a mixture of water (20 mL), methanol (20 mL), and concentrated HCl (40 mL), and heated (bath temperature: 90° C.) under reflux for 3 hours. The reaction mixture is cooled, filtered and evaporated, and the residue is dissolved in hot 1N HCl. The solution is filtered, the filtrate is evaporated, and the residue is stripped with isopropanol (twice) and ethanol (twice). The residue is dissolved in ethanol, ether is added, and upon evaporation of the solvent, there is obtained 1,12-diamino-6,6-difluoro-4,9-di-p-toluenesulfonyl-4,9-diaza-dodecane as a white crystalline foam: 2.7 g (quantitative yield).

Workup

  1. customEvaporation
  2. customyields a residue which
  3. temperatureheated (bath temperature: 90° C.)
  4. temperatureunder reflux for 3 hours
  5. temperatureThe reaction mixture is cooled
  6. filtrationfiltered
  7. customevaporated
  8. dissolutionthe residue is dissolved in hot 1N HCl
  9. filtrationThe solution is filtered
  10. customthe filtrate is evaporated
  11. dissolutionThe residue is dissolved in ethanol
  12. additionether is added
  13. customupon evaporation of the solvent

Sources & evidence

ORD record
ord-70621dde59664439874a1a47bf1f1476
Source dataset
uspto-grants-1988_10
Patent number
US04778926

Reaction notes

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