Ammonium Chloride → (-)-4-Benzo[b]thiophen-5-yl-2-methyl-1,2,3,4-tetrahydroisoquinoline-7-ol

HRID 1517037Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1517037
[S:1]1[CH:5]=[CH:4][C:3]2[CH:6]=[C:7]([CH:10]3[C:19]4[C:14](=[CH:15][C:16]([O:20]C)=[CH:17][CH:18]=4)[CH2:13][N:12]([CH3:22])[CH2:11]3)[CH:8]=[CH:9][C:2]1=2.C([S-])C.[Na+].[NH4+].[Cl-]>CN(C=O)C>[S:1]1[CH:5]=[CH:4][C:3]2[CH:6]=[C:7]([CH:10]3[C:19]4[C:14](=[CH:15][C:16]([OH:20])=[CH:17][CH:18]=4)[CH2:13][N:12]([CH3:22])[CH2:11]3)[CH:8]=[CH:9][C:2]1=2

Komponenten

5

Edukt 3

HCID 25517Ammonium ChlorideHCID 4459711Sodium ethanethiolateHCID 689943124-Benzo[b]thiophen-5-yl-7-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline

Produkt 1

HCID 68997664(-)-4-Benzo[b]thiophen-5-yl-2-methyl-1,2,3,4-tetrahydroisoquinoline-7-olAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
140 °C

Versuchsvorschrift

A mixture of (−)-4-benzo[b]thiophen-5-yl-7-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline (10.00 g, 32.3 mmol) which was obtained according to Step F in the preparation of Example 98 and sodium ethanethiolate (11.3 g, 134.3 mmol) in DMF (250 mL) was heated at 140° C. under an N2 atmosphere for 14 hours. The reaction mixture was cooled in an ice bath before addition of saturated NH4Cl (250 mL). The aqueous phase was extracted with DCM (3×750 mL) and the combined organic extracts washed with water (3×500 mL), brine, dried over Na2SO4 and concentrated in vacuo. The crude material was purified by silica gel column chromatography (eluent: 5% MeOH/CH2Cl2) to afford (−)-4-benzo[b]thiophen-5-yl-2-methyl-1,2,3,4-tetrahydroisoquinoline-7-ol (6.64 g, 70%) as an orange-brown solid: 1H NMR (300 MHz, CDCl3) δ 7.76 (d, J=8.3 Hz, 1H), 7.62 (s, 1H), 7.40 (d, J=5.4 Hz, 1H), 7.26-7.20 (m, 2H), 7.13 (d, J=8.4 Hz, 1H), 6.66 (d, J=8.3 Hz, 1H), 6.50-6.40 (m, 2H), 4.34 (dd, J=9.0, 6.0 Hz, 1H), 3.68 (d, J=15.0 Hz, 1H), 3.54 (d, J=15.0 Hz, 1H), 3.11 (dd, J=11.5, 5.7 Hz, 1H), 2.58 (dd, J=11.3, 9.7 Hz, 1H), 2.43 (s, 3H); ESI-MS m/z=296 [M+H]+.

Aufarbeitung

  1. customwas obtained
  2. extractionThe aqueous phase was extracted with DCM (3×750 mL)
  3. washthe combined organic extracts washed with water (3×500 mL), brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe crude material was purified by silica gel column chromatography (eluent: 5% MeOH/CH2Cl2)

Quellen und Nachweise

ORD-Eintrag
ord-d60acf73666d40a39d41a4a1031e3023
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08227486B2

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