3,4-Dibromothiophene → 3-Bromo-4(trimethylsiloxypropynyl)thiophene

HRID 1686169

Reaktionsgleichung

Reaktionsgleichung von HRID 1686169
Br[C:2]1[C:6]([Br:7])=[CH:5][S:4][CH:3]=1.[CH3:8][Si:9]([CH3:15])([CH3:14])[O:10][CH2:11][C:12]#[CH:13]>[Cu](I)I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>[Br:7][C:6]1[C:2]([C:13]#[C:12][CH2:11][O:10][Si:9]([CH3:15])([CH3:14])[CH3:8])=[CH:3][S:4][CH:5]=1

Komponenten

6

Edukt 2

HCID 184523,4-DibromothiopheneHCID 79696Silane, trimethyl(2-propyn-1-yloxy)-

Produkt 1

HCID 577344533-Bromo-4(trimethylsiloxypropynyl)thiopheneAusbeute 19,6 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11776TriphenylphosphineKatalysatorHCID 83717Copper iodideKatalysatorHCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

Into a 250 mL 4 necked RB flask equipped with a magnetic stirring bar, thermometer, rubber septum, argon inlet and reflux condenser with argon outlet (tubed to a silicon oil bubbler) is added 48.3 g (229 mmol) of 3,4-dibromothiophene, 13.0 g of triethylamine, 20.1 g (157 mmol) of 3-trimethylsiloxypropyne, 130 mg of triphenylphosphine, 147 mg of copper iodide and 470 mg of dichlorobis(triphenylphosphine) palladium(II). The mixture is heated with a silicon oil bath to 70° C. under argon with stirring for 5.5 hrs. The cooled mixture is then concentrated on a rotary evaporator at reduced pressure and the residue taken up in 200 mL of hexanes and washed with 2×25 mL of water and the pentane phase dried over sodium sulfate and then concentrated on a rotary evaporator. The residue was chromatographed through neutral silica gel eluted with 2/1 methylene chloride/ethyl acetate to yield 8.9 g of 3-bromo-4(trimethylsiloxypropynyl)thiophene as a light yellow oil which was used directly to prepare 2-hydroxymethylselenolo[2,3-c]thiophene.

Aufarbeitung

  1. temperaturethermometer, rubber septum, argon inlet and reflux condenser with argon outlet (
  2. concentrationThe cooled mixture is then concentrated on a rotary evaporator at reduced pressure
  3. washwashed with 2×25 mL of water
  4. dry with materialthe pentane phase dried over sodium sulfate
  5. concentrationconcentrated on a rotary evaporator
  6. customThe residue was chromatographed through neutral silica gel
  7. washeluted with 2/1 methylene chloride/ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-eb94742759a941b0b46a138690cd6e3f
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08148548B2

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