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

HRID 1526736ノート

反応式

HRID 1526736 の反応式
[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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
140 °C

実験手順

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]+.

後処理

  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)

出典と根拠

ORDレコード
ord-81ad67a96d3c45a998d03f9429a7a4f7
出典データセット
uspto-grants-2015_07
特許番号
US09085531B2

反応ノート

読み込み中…