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Chloroform → 1-methoxy-6,7,8,9-tetrahydro-5H-benzo[7]annulen-6-one

HRID 2276302
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2276302
[CH3:1][O:2][C:3]1[CH:12]=[CH:11][CH:10]=[C:9]2[C:4]=1[CH2:5][CH2:6][CH2:7][C:8]2=[CH2:13].O.O.O.[N+]([O-])([O-])=[O:18].[Tl+3].[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.C(Cl)(Cl)Cl>CO>[CH3:1][O:2][C:3]1[C:4]2[CH2:5][CH2:6][CH2:7][C:13](=[O:18])[CH2:8][C:9]=2[CH:10]=[CH:11][CH:12]=1
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Komponenten

5

Edukt 3

HCID 6212ChloroformHCID 11270721Nitric acid,thallium(3+) salt, trihydrate (9CI)HCID 116080075-Methoxy-1-methylene-1,2,3,4-tetrahydronaphthalene

Produkt 1

HCID 127282361-methoxy-6,7,8,9-tetrahydro-5H-benzo[7]annulen-6-one

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel2×

Versuchsvorschrift

5-Methoxy-1-methylene-1,2,3,4-tetrahydro-naphthalene (23.8 g, 0.137 mol) in 150 mL MeOH added in one portion to freshly prepared solution of thallium(III)nitrate trihydrate (1.0 eq) in 300 mL MeOH. Stirred one minute and 400 mL chloroform added. The solution was filtered and the organics partitioned between dichloromethane and water. The organics were dried (MgSO4) and concentrated. Purification by chromatography (ISCO, 330 g silica cartridge; stepwise elution hexane (5 min) then 7 minute gradient to 100% dichloromethane (20 min) affords the title compound as the most polar of the products as a pale yellow oil (26 g, 97%). 1H-NMR (400 MHz, CDCl3) 7.16 (t, J=7.9 Hz, 1H), 7.84 (d, J=8.3 Hz, 1H), 6.79 (d, J=7.5 Hz, 1H), 3.84 (s, 3H), 3.73 (s, 2H), 3.05-3.01 (m, 2H), 2.55 (t, J=7.0 Hz, 2H), 2.01-1.96 (m, 2H). LC/MS (ESI+) m/z=191 (M+H)+

Aufarbeitung

  1. filtrationThe solution was filtered
  2. customthe organics partitioned between dichloromethane and water
  3. dry with materialThe organics were dried (MgSO4)
  4. concentrationconcentrated
  5. customPurification by chromatography (ISCO, 330 g silica cartridge
  6. washstepwise elution hexane (5 min)

Quellen und Nachweise

ORD-Eintrag
ord-1d5dfea5e09945ed8f64588eb6bbe7f3
Quelldatensatz
uspto-grants-2015_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09132128B2

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