Water → 1,2,2a,3,4,5-Hexahydroacenaphthylen-1-amine

HRID 331225Notes

Reaction equation

HRID 331225 reaction equation
[CH:1]1(O)[C:11]2=[C:12]3[C:7](=[CH:8][CH:9]=[CH:10]2)[CH2:6][CH2:5][CH2:4][CH:3]3[CH2:2]1.C1(P([N:28]=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.C1(C2CCCCCCCCCC=2)CCCCCCCCNN=1.O>C1(C)C=CC=CC=1>[CH:1]1([NH2:28])[C:11]2=[C:12]3[C:7](=[CH:8][CH:9]=[CH:10]2)[CH2:6][CH2:5][CH2:4][CH:3]3[CH2:2]1

Participants

6

Reactant 4

HCID 962WaterHCID 199401P,P-Diphenylphosphinic azideHCID 2652581,2,2a,3,4,5-Hexahydroacenaphthylen-1-olHCID 536302743-(Cycloundecen-1-yl)-1,2-diazacycloundec-2-ene

Product 1

HCID 638213741,2,2a,3,4,5-Hexahydroacenaphthylen-1-amine

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a cooled (0° C.) solution of 2a,3,4,5-tetrahydro-2H-acenaphthylen-1-ol and diphenylphosphoryl azide (9.31 g) in toluene (90 ml) was added DBU (diazabicycloundecene) (5.04 mL), and the mixture was stirred at room temperature for 3 hr. The reaction mixture was poured into water, and the mixture was extracted with toluene. The combined organic layer was washed with water, dried over magnesium sulfate, and concentrated. The crude product was dissolved in a mixed solvent (77 ml) of THF/water (10:1), triphenylphosphine (9.61 g) was added, and the mixture was heated under reflux for 1 hr. After cooling to room temperature, the solvent was evaporated, 1N hydrochloric acid (100 ml) was added to the residue, and unnecessary substances were removed by extraction with ethyl acetate. The aqueous phase was alkalified with potassium carbonate, and extracted with chloroform. The extract was washed with water and saturated brine, dried over magnesium sulfate, and concentrated to give 1,2,2a,3,4,5-hexahydroacenaphthylen-1-ylamine.

Workup

  1. extractionthe mixture was extracted with toluene
  2. washThe combined organic layer was washed with water
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated
  5. dissolutionThe crude product was dissolved in a mixed solvent (77 ml) of THF/water (10:1), triphenylphosphine (9.61 g)
  6. additionwas added
  7. temperaturethe mixture was heated
  8. temperatureunder reflux for 1 hr
  9. temperatureAfter cooling to room temperature
  10. customthe solvent was evaporated
  11. addition1N hydrochloric acid (100 ml) was added to the residue, and unnecessary substances
  12. customwere removed by extraction with ethyl acetate
  13. extractionextracted with chloroform
  14. washThe extract was washed with water and saturated brine
  15. dry with materialdried over magnesium sulfate
  16. concentrationconcentrated

Sources & evidence

ORD record
ord-6c9b2076cce943e9854a2bce218aca26
Source dataset
uspto-grants-2014_11
Patent number
US08877779B2

Reaction notes

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