3-Chloro-5-fluorobenzo[b]thiophene-2-carbonyl chloride → (3-Chloro-7-fluoro-benzo[b]thiophen-2-yl)methanol

HRID 1362304Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1362304
ClC1C2C=C(F)C=CC=2SC=1C(Cl)=O.[Cl:15][C:16]1[C:17]2[CH:27]=[CH:26][CH:25]=[C:24]([F:28])[C:18]=2[S:19][C:20]=1[C:21](Cl)=[O:22].[H-].[Al+3].[Li+].[H-].[H-].[H-]>C1COCC1>[Cl:15][C:16]1[C:17]2[CH:27]=[CH:26][CH:25]=[C:24]([F:28])[C:18]=2[S:19][C:20]=1[CH2:21][OH:22]

Komponenten

5

Edukt 3

HCID 148724863-Chloro-5-fluorobenzo[b]thiophene-2-carbonyl chlorideHCID 21226445Aluminium lithium hydrideHCID 592776183-Chloro-7-fluoro-benzo[b]thiophene-2-carbonyl chloride

Produkt 1

HCID 59277539(3-Chloro-7-fluoro-benzo[b]thiophen-2-yl)methanolAusbeute 11,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To an ice-cold suspension of a 6:1 mixture of 3-chloro-5-fluoro-benzo[b]thiophene-2-carbonyl chloride and 3-chloro-7-fluoro-benzo[b]thiophene-2-carbonyl chloride (5.46 g, 23.6 mmol) in THF (120 mL) was added lithium aluminum hydride (11.8 mL of a 1.0 M solution in THF, 11.8 mmol) dropwise. The mixture was stirred for 4 h then quenched with NaOH (0.35 N solution in H2O). The mixture was diluted with Et2O and the solution filtered. The filtrate was dried (Na2SO4) and concentrated. Purification by flash column chromatography (silica gel, hexanes/EtOAc, 9:1 to hexanes/EtOAc 8:2) gave the title compound (600 mg, 4% (2 steps), 7-fluoro isomer) as a light, yellow solid: 1H NMR (300 MHz, CDCl3) δ 7.59 (d, J=8.0 Hz, 1H), 7.41 (ddd, J=8.0, 8.0, 4.9 Hz, 1H), 7.10 (dd, J=9.1, 9.1 Hz, 1H), 5.00 (d, J=6.2 Hz, 2H), 2.04 (t, J=6.5 Hz, 1H).

Aufarbeitung

  1. customthen quenched with NaOH (0.35 N solution in H2O)
  2. additionThe mixture was diluted with Et2O
  3. filtrationthe solution filtered
  4. dry with materialThe filtrate was dried (Na2SO4)
  5. concentrationconcentrated
  6. customPurification by flash column chromatography (silica gel, hexanes/EtOAc, 9:1 to hexanes/EtOAc 8:2)

Quellen und Nachweise

ORD-Eintrag
ord-e81ea9ee8e9d4bbfa0f24d07154879a5
Quelldatensatz
uspto-grants-2011_02
Patentnummer
US07879872B2

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