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

HRID 1672528노트

반응식

HRID 1672528 반응식
[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]

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 935Nickel촉매HCID 702Ethanol용매HCID 6344Dichloromethane용매

반응 조건

온도
85 °C

실험 절차

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)+.

후처리

  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)

출처 및 근거

ORD 기록
ord-158a4bddec534a57a99a23ccd5c6a7e3
출처 데이터셋
uspto-grants-2011_08
특허 번호
US07998993B2

반응 노트

불러오는 중…