8-Amino-2-naphthalenol → 8-Amino-1,2,3,4-tetrahydronaphthalen-2-ol

HRID 1672540Notes

Reaction equation

HRID 1672540 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[CH:10]=[C:9]([OH:12])[CH:8]=[CH:7]2.[OH-].[Na+]>[Ni].C(O)C>[NH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[CH2:10][CH:9]([OH:12])[CH2:8][CH2:7]2

Participants

5

Reactant 2

HCID 83588-Amino-2-naphthalenolHCID 14798Sodium Hydroxide

Product 1

HCID 230669958-Amino-1,2,3,4-tetrahydronaphthalen-2-olYield 37.2%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Conditions

Temperature
85 °C

Procedure

Ethanol (1 liter) was added to 8-amino-2-naphthol (100 g, 0.61 mol), Raney nickel (40 g water wet), and sodium hydroxide (4.0 g 8 mol % aqueous) in a stirred reactor. The reactor was sealed and sparged with hydrogen. The reaction mixture was stirred for 13 hours at 85° C. and then an additional 8 hours at 100° C. The mixture was then filtered through a pad of Celite. The resulting solution was treated with Darco G-60 (35 grams) and heated to reflux for 1 hour, then cooled to ambient temperature and stirred an additional 3 hours. This mixture was filtered through Celite (350 grams), and the pad washed with ethyl acetate (1.5 liters). The solvent was removed in vacuo and methyl tert-butyl ether (1 liter) was added. This was heated for 15 minutes at 50° C., stirred for one hour at ambient temperature, filtered, and the solvent removed in vacuo. Approximately half of the resulting crude solid was purified by chromatography on silica gel using 2% to 30% methanol/methylene chloride as eluent, which gave 37 g of the title compound as a light brown solid. 1H NMR (300 MHz, CDCl3) δ 6.96 (t, J=7.63 Hz, 1H), 6.55 (dd, J=10.68, 7.63 Hz, 2H), 4.14-4.24 (m, 1H), 2.80-2.95 (m, 3H), 2.38 (dd, J=16.11, 7.63 Hz, 1H), 1.96-2.09 (m, 1H), 1.70-1.85 (m, 1H).

Workup

  1. customThe reactor was sealed
  2. customsparged with hydrogen
  3. customan additional 8 hours
  4. customat 100° C
  5. filtrationThe mixture was then filtered through a pad of Celite
  6. additionThe resulting solution was treated with Darco
  7. temperature(35 grams) and heated
  8. temperatureto reflux for 1 hour
  9. temperaturecooled to ambient temperature
  10. stirringstirred an additional 3 hours
  11. filtrationThis mixture was filtered through Celite (350 grams)
  12. washthe pad washed with ethyl acetate (1.5 liters)
  13. customThe solvent was removed in vacuo and methyl tert-butyl ether (1 liter)
  14. additionwas added
  15. temperatureThis was heated for 15 minutes at 50° C.
  16. stirringstirred for one hour at ambient temperature
  17. filtrationfiltered
  18. customthe solvent removed in vacuo
  19. customApproximately half of the resulting crude solid was purified by chromatography on silica gel using 2% to 30% methanol/methylene chloride as eluent

Sources & evidence

ORD record
ord-8f410d347e8d47ca9c77921ff231fe9c
Source dataset
uspto-grants-2011_08
Patent number
US07998993B2

Reaction notes

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