2-Chloro-4'-fluoropropiophenone → 1-Chloro-3-(4-fluorophenyl)hex-5-en-3-ol

HRID 450961

Reaktionsgleichung

Reaktionsgleichung von HRID 450961
[CH2:1]([Mg]Br)[CH:2]=[CH2:3].[Cl:6][CH2:7][CH2:8][C:9]([C:11]1[CH:16]=[CH:15][C:14]([F:17])=[CH:13][CH:12]=1)=[O:10]>C1COCC1>[Cl:6][CH2:7][CH2:8][C:9]([C:11]1[CH:12]=[CH:13][C:14]([F:17])=[CH:15][CH:16]=1)([OH:10])[CH2:3][CH:2]=[CH2:1]

Komponenten

4

Edukt 2

HCID 676722-Chloro-4'-fluoropropiophenoneHCID 178455850HCID 178455850, Verbindung

Produkt 1

HCID 534729381-Chloro-3-(4-fluorophenyl)hex-5-en-3-olAusbeute 97,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

A 250-mL flask was charged with anhydrous CeCl3 (5.58 g, 22.6 mmol) and THF (40 mL). The mixture was vigorously stirred for 3.5 h at rt. The suspension was then cooled to −78° C. and a solution of allylmagnesium bromide (1.0 M in THF, 21 mL, 21.0 mmol) was added. After stirring for 2 h at −78° C., a solution of 3-chloro-1-(4-fluorophenyl)propan-1-one (2.522 g, 13.5 mmol) in THF (30 mL) was added via cannula. The reaction mixture was allowed to slowly warm to 8° C. while stirring overnight (18 h). The reaction was then quenched with satd aq NaHCO3, extracted with EtOAc, and dried over Na2SO4. After the solvents were evaporated, the residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford of 1-chloro-3-(4-fluorophenyl)hex-5-en-3-ol (3.0049 g, 97%) as an oil. LC-MS Method 1 tR=1.79 min, m/z 213, 211 (M-OH)+; 1H NMR (400 MHz, CDCl3) δ 7.37-7.32 (m, 2H), 7.07-7.02 (m, 2H), 5.57-5.47 (m, 1H), 5.20-5.19 (m, 1H), 5.16 (m, 1H), 3.59-3.52 (m, 1H), 3.24-3.18 (m, 1H), 2.70 (dd, J=13.8, 5.9 Hz, 1H), 2.50 (dd, J=13.8, 8.5 Hz, 1H), 2.29 (t, J=7.9 Hz, 2H), 2.22 (s, 1H); 19F NMR (376 MHz, CDCl3) δ −116.52 (m).

Aufarbeitung

  1. temperatureThe suspension was then cooled to −78° C.
  2. stirringAfter stirring for 2 h at −78° C.
  3. temperatureto slowly warm to 8° C.
  4. stirringwhile stirring overnight (18 h)
  5. customThe reaction was then quenched with satd aq NaHCO3
  6. extractionextracted with EtOAc
  7. dry with materialdried over Na2SO4
  8. customAfter the solvents were evaporated
  9. customthe residue was purified by chromatography on silica gel
  10. washeluted with hexanes/ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-5f2248bfcd1a4e699aa7fb5242f9bc6b
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08487094B2

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