Tin tetrachloride → {1-Bromo-6-[3-(3,3-dimethyl-butyryl)-benzo[b]thiophen-2-yl]-naphthalen-2-yloxy}-acetic acid ethyl ester

HRID 1373874Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1373874
[CH2:1]([O:3][C:4](=[O:27])[CH2:5][O:6][C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:17]3[S:21][C:20]4[CH:22]=[CH:23][CH:24]=[CH:25][C:19]=4[CH:18]=3)[CH:13]=2)[C:8]=1[Br:26])[CH3:2].[C:28]([CH2:32][C:33](Cl)=[O:34])([CH3:31])([CH3:30])[CH3:29].[Sn](Cl)(Cl)(Cl)Cl>C(Cl)(Cl)Cl>[CH2:1]([O:3][C:4](=[O:27])[CH2:5][O:6][C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:17]3[S:21][C:20]4[CH:22]=[CH:23][CH:24]=[CH:25][C:19]=4[C:18]=3[C:33](=[O:34])[CH2:32][C:28]([CH3:31])([CH3:30])[CH3:29])[CH:13]=2)[C:8]=1[Br:26])[CH3:2]

Komponenten

5

Edukt 3

HCID 24287Tin tetrachloride2×HCID 815143,3-Dimethylbutanoyl chloride2×HCID 69410849HCID 69410849, Verbindung

Produkt 1

HCID 69411486{1-Bromo-6-[3-(3,3-dimethyl-butyryl)-benzo[b]thiophen-2-yl]-naphthalen-2-yloxy}-acetic acid ethyl esterAusbeute 6,53 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6212ChloroformLösungsmittel2×

Versuchsvorschrift

To a 0° C. mixture of (6-benzo[b]thiophen-2-yl-1-bromo-naphthalen-2-yloxy)-acetic acid ethyl ester (5.18 g, 11.7 mmol) in chloroform (270 mL) was added t-butylacetyl chloride (2.0 mL, 14 mmol) and tin (IV) chloride (2.1 mL, 18 mmol). It was refluxed for 23 hours. During reflux, more t-butylacetyl chloride (9.0 mL, 66 mmol) in four portions and tin (IV) chloride (8.4 mL, 71 mmol) in four portions were added. It was then allowed to cool to ambient temperature and poured into ice water. It was diluted with additional chloroform and washed with water and brine. It was then dried with anhydrous magnesium sulfate, filtered and solvent evaporated. The residue was purified by flash chromatography using (1) 100% chloroform, (2) 25–60% methylene chloride in hexane. It was then purified by HPLC using 90% acetonitrile (0.1% trifluoroacetic acid) in water as the mobile phase. Evaporating the solvent and extracting with ethyl acetate, washing with water and brine, drying with anhydrous magnesium sulfate, filtering, concentrating and drying in vacuo at ambient temperature for two hours yielded {1-bromo-6-[3-(3,3-dimethyl-butyryl)-benzo[b]thiophen-2-yl]-naphthalen-2-yloxy}-acetic acid ethyl ester as an amber semi-solid (0.412 g, 6.53%); mass spectrum (+EI, [M+H]+) m/z 539/541. 1H NMR (500 MHz, DMSO-d6): δ8.26 (d, 1H, J=8.81 Hz), 8.07–8.14(m, 3H), 7.91–7.93 (m, 1H), 7.76 (dd, 1H, J=8.81 Hz and 1.97 Hz), 7.45–7.53 (m, 3H), 5.12 (s, 2H), 4.19 (q, 2H, J=7.15 Hz), 2.33 (s, 2H), 1.20–1.25 (m, 3H), 0.76 ppm (s, 9H). Elemental Analysis for C28H27BrNO4S: Calcd: C, 62.34; H, 5.04; N, 0.00; Found: C, 57.16; H, 4.37; N, 0.00.

Aufarbeitung

  1. temperatureIt was refluxed for 23 hours
  2. temperatureDuring reflux
  3. washwashed with water and brine
  4. dry with materialIt was then dried with anhydrous magnesium sulfate
  5. filtrationfiltered
  6. customsolvent evaporated
  7. customThe residue was purified by flash chromatography
  8. customIt was then purified by HPLC
  9. customEvaporating the solvent
  10. extractionextracting with ethyl acetate
  11. washwashing with water and brine
  12. dry with materialdrying with anhydrous magnesium sulfate
  13. filtrationfiltering
  14. concentrationconcentrating
  15. customdrying in vacuo at ambient temperature for two hours

Quellen und Nachweise

ORD-Eintrag
ord-6a2cd4883b284ddcafb907aca9a46231
Quelldatensatz
uspto-grants-2007_01
Patentnummer
US07163954B2

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