Ethanol → HCID 13935588, compound

HRID 232168Notes

Reaction equation

HRID 232168 reaction equation
C1(=O)[N:5]([CH2:6][CH2:7][CH2:8][N:9]([S:27]([C:30]2[CH:35]=[CH:34][C:33]([CH3:36])=[CH:32][CH:31]=2)(=[O:29])=[O:28])[CH2:10][CH2:11][C:12]([F:26])([F:25])[CH2:13][N:14]2C(=O)C3=CC=CC=C3C2=O)C(=O)C2=CC=CC=C12.O.NN.C(O)C.[OH-].[Na+]>O.Cl.CC(C)=O>[NH2:5][CH2:6][CH2:7][CH2:8][N:9]([S:27]([C:30]1[CH:31]=[CH:32][C:33]([CH3:36])=[CH:34][CH:35]=1)(=[O:29])=[O:28])[CH2:10][CH2:11][C:12]([F:25])([F:26])[CH2:13][NH2:14]

Participants

8

Reactant 4

HCID 702EthanolHCID 14798Sodium HydroxideHCID 24654Hydrazine hydrate (1:1)HCID 13935587HCID 13935587, compound

Product 1

HCID 13935588HCID 13935588, compound

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

The compound 1,8-diphthalimido-4-p-toluenesulfonyl-7,7-difluoro-4-aza-octane (58.95 g, 99.07 moles) and 1M hydrazine hydrate in ethanol (235 mL, 235 mmoles) are stirred and heated at 90° C. overnight. Conc. HCl (150 mL) is added, and heating (90° C.) and stirring are continued for 45 min. After cooling to room temperature, phthalhydrazide is removed by filtration, and the solvent is evaporated. The residue is dissolved in water, the solution is filtered and evaporated to yield a residue which solidifies upon stripping with acetone. This material is dissolved in water (300 mL), aqueous NaOH (25 g NaOH/150 mL water) is added, and the mixture is extracted with dichloromethane (3×400 mL). Washing with water (200 mL), drying (Na2SO4) and evaporation of the solvent yields a yellow oil, 35.0 g, which is dissolved in 6N HCl (300 mL), evaporated, and stripped with ethanol (twice), CCl4 (twice) and acetone (twice) to yield 1,8-diamino-4 -p-toluenesulfonyl-7,7-difluoro-4-aza-octane as a white solid. This compound is recrystallized by dissolving in the minimum amount of methanol and the addition of acetone/ether: 31.3 g (78%).

Workup

  1. temperatureheating (90° C.)
  2. temperatureAfter cooling to room temperature
  3. customphthalhydrazide is removed by filtration
  4. customthe solvent is evaporated
  5. dissolutionThe residue is dissolved in water
  6. filtrationthe solution is filtered
  7. customevaporated
  8. customto yield a residue which
  9. extractionthe mixture is extracted with dichloromethane (3×400 mL)
  10. washWashing with water (200 mL)
  11. customdrying
  12. custom(Na2SO4) and evaporation of the solvent
  13. customyields a yellow oil, 35.0 g, which
  14. customevaporated

Sources & evidence

ORD record
ord-b219333c5f364ed48a5d29d28515ae2c
Source dataset
uspto-grants-1989_07
Patent number
US04851448

Reaction notes

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