Hydrogen Bromide → 6,6-Difluorospermine

HRID 2413851Notes

Reaction equation

HRID 2413851 reaction equation
[NH2:1][CH2:2][CH2:3][CH2:4][N:5](S(C1C=CC(C)=CC=1)(=O)=O)[CH2:6][C:7]([F:26])([F:25])[CH2:8][CH2:9][N:10](S(C1C=CC(C)=CC=1)(=O)=O)[CH2:11][CH2:12][CH2:13][NH2:14].Br>CC(C)=O>[F:25][C:7]([F:26])([CH2:8][CH2:9][NH:10][CH2:11][CH2:12][CH2:13][NH2:14])[CH2:6][NH:5][CH2:4][CH2:3][CH2:2][NH2:1]

Participants

4

Reactant 2

HCID 260Hydrogen BromideHCID 21288462HCID 21288462, compound

Product 1

HCID 1306786,6-Difluorospermine

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

The compound 1,12-diamino-6,6-difluoro-4,9-di-p-toluenesulfonyl-4,9-diaza-dodecane (2.7 g, 4.36 mM) and 47% aqueous HBr are refluxed (bath temperature: 110° C.) for 17 hours. After cooling to room temperature, the solution is carefully extracted with ether (three times) and finally with chloroform. Evaporation of the aqueous phase, followed by stripping with isopropanol (twice) and ethanol (twice) produces a solid residue which is digested with acetone, collected, and washed with acetone (three times), ethanol (three times) and finally with ether: white crystals, 1.8 g (74%). This material is recrystallized by dissolving in hot (80° C.) aqueous ethanol (100 mL, H2O: ethanol 1:9), filtering through paper, and adding additional ethanol (10-20 mL) to yield the desired 6,6-difluoro-1,12-diamino-4,9-diaza-dodecane as the tetrahydrobromide salt: white crystals 1.2 g, (49%).

Workup

  1. extractionthe solution is carefully extracted with ether (three times) and finally with chloroform
  2. customEvaporation of the aqueous phase
  3. customproduces a solid residue which
  4. customcollected
  5. washwashed with acetone (three times), ethanol (three times) and finally with ether
  6. customThis material is recrystallized
  7. dissolutionby dissolving in hot (80° C.) aqueous ethanol (100 mL, H2O: ethanol 1:9)
  8. filtrationfiltering through paper
  9. additionadding additional ethanol (10-20 mL)

Sources & evidence

ORD record
ord-071f313a2ac74e0a9767caf2528f2f68
Source dataset
uspto-grants-1988_01
Patent number
US04719313

Reaction notes

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