Imidazole → 7-{[Tert-butyl(dimethyl)silyl]oxy}-5,6,7,8-tetrahydronaphthalen-1-amine

HRID 1672528Notes

Reaction equation

HRID 1672528 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+].N1C=CN=C1.[C:20]([Si:24](Cl)([CH3:26])[CH3:25])([CH3:23])([CH3:22])[CH3:21]>[Ni].C(O)C.C(Cl)Cl>[Si:24]([O:12][CH:9]1[CH2:10][C:11]2[C:2]([NH2:1])=[CH:3][CH:4]=[CH:5][C:6]=2[CH2:7][CH2:8]1)([C:20]([CH3:23])([CH3:22])[CH3:21])([CH3:26])[CH3:25]

Participants

8

Reactant 4

HCID 795ImidazoleHCID 83588-Amino-2-naphthalenolHCID 14798Sodium HydroxideHCID 28928tert-Butyldimethylsilyl chloride

Product 1

HCID 587341927-{[Tert-butyl(dimethyl)silyl]oxy}-5,6,7,8-tetrahydronaphthalen-1-amine

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of 8-amino-2-naphthol (47.55 g, 298.7 mmol), Raney nickel (20.20 g), and 50% aq. NaOH (1.97 g) in ethanol (480 mL) in a sealed reactor was purged three times (3×40 psi H2/vacuum cycles), then the reactor was pressurized with 1300 psi H2 and heated at 85° C. for 7 hours. After this time, the catalyst was filtered off (Celite), and the filtrate was evaporated to afford a dark oil. The oil was dissolved in CH2Cl2 (600 mL) and was treated with imidazole (65.9 g, 969 mmol) and tert-butylchlorodimethylsilane (59.0 g, 392 mmol). The reaction mixture was stirred at room temperature for 18 hours, and washed with water and brine. The organic solution was dried over Na2SO4 and evaporated. The residue was chromatographed on silica gel (9:1 to 4:1 hexane-ethyl acetate, eluant) to afford the title compound as a dark purple oil, 44.22 g (49%). 1H NMR (300 MHz, DMSO-d6) δ 6.76 (m, 1H), 6.40 (m, 1H), 6.27 (d, J=7.5 Hz, 1H), 4.68 (br, 2H), 4.07 (m, 1H), 2.57-2.79 (m, 3H), 2.22 (m, 1H), 1.81 (m, 1H), 1.58 (m, 1H), 0.87 (s, 9H), 0.08 (s, 6H). MS (ESI+) m/z 278 (M+H)+.

Workup

  1. customwas purged three times (3×40 psi H2/vacuum cycles)
  2. filtrationAfter this time, the catalyst was filtered off (Celite)
  3. customthe filtrate was evaporated
  4. customto afford a dark oil
  5. washwashed with water and brine
  6. dry with materialThe organic solution was dried over Na2SO4
  7. customevaporated
  8. customThe residue was chromatographed on silica gel (9:1 to 4:1 hexane-ethyl acetate, eluant)

Sources & evidence

ORD record
ord-158a4bddec534a57a99a23ccd5c6a7e3
Source dataset
uspto-grants-2011_08
Patent number
US07998993B2

Reaction notes

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