Dichloromethane → Methyl [4-bromo-2-(4-propoxyphenyl)thien-3-yl]acetate

HRID 2373702Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2373702
Br[C:2]1[S:3][CH:4]=[C:5]([Br:12])[C:6]=1[CH2:7][C:8]([O:10][CH3:11])=[O:9].[CH2:13]([O:16][C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][CH:18]=1)[CH2:14][CH3:15].C([O-])([O-])=O.[K+].[K+].ClCCl>O.CCOC(C)=O.CCCCCC.O1CCOCC1>[Br:12][C:5]1[C:6]([CH2:7][C:8]([O:10][CH3:11])=[O:9])=[C:2]([C:20]2[CH:21]=[CH:22][C:17]([O:16][CH2:13][CH2:14][CH3:15])=[CH:18][CH:19]=2)[S:3][CH:4]=1

Komponenten

9

Edukt 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 44564904-Propoxyphenylboronic AcidHCID 86607173Methyl (2,4-dibromothien-3-yl)acetate

Produkt 1

HCID 86607172Methyl [4-bromo-2-(4-propoxyphenyl)thien-3-yl]acetateAusbeute 57,5 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 962WaterLösungsmittelHCID 8058HexaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 312751,4-DioxaneLösungsmittel2×

Versuchsvorschrift

Into dioxane (3 mL) was dissolved methyl (2,4-dibromothien-3-yl)acetate (0.355 g, 1.13 mmol) and 4-propoxyphenylboronic acid (0.214 g, 1.19 mmol). K2CO3 (0.195 g, 1.41 mmol) was dissolved in H2O (0.4 mL) and added to the dioxane. The solution was degassed by bubbling argon through the mixture for five minutes. {1,1′-Bis(diphenylphosphino)-ferrocene}dichloropalladium(II) complex with dichloromethane (1:1) (0.027 g, 0.033 mmol) was added and the mixture heated under argon to 50° C. for 4 hours (followed by TLC 15:1 Hexane:EtOAc). The solvents were removed and the mixture partitioned between EtOAc and H2O. The EtOAc layer was dried (MgSO4) and absorbed onto silica gel. The product was purified by flash chromatography (25:1 hexane:EtOAc) to yield methyl [4-bromo-2-(4-propoxyphenyl)thien-3-yl]acetate (0.240 g) as a clear oil. 1H NMR (500 MHz, DMSO-d6) δ: 0.99 (t, 3H, J=7.32 Hz), 1.75 (m, 2H), 3.65 (s, 5H), 3.98 (t, 2H, J=6.6 Hz), 7.05 (d, 2H, J=8.2 Hz), 7.33 (d, 2H, J=8.2 Hz), 7.72 (s, 1H). MS (ES) m/z 369.0 ([M+H]+). MS (ES) m/z 386.0 ([M+NH4]+).

Aufarbeitung

  1. customThe solution was degassed
  2. customby bubbling argon through the mixture for five minutes
  3. customThe solvents were removed
  4. customthe mixture partitioned between EtOAc and H2O
  5. dry with materialThe EtOAc layer was dried (MgSO4)
  6. customabsorbed onto silica gel
  7. customThe product was purified by flash chromatography (25:1 hexane:EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-b620c22040d74cdd992425de555f8416
Quelldatensatz
uspto-grants-2008_12
Patentnummer
US07459567B2

Notizen zur Reaktion

Wird geladen…