N-Phenyl-2-benzyloxyethylamine → 9-(2-Benzyloxy-ethyl)-2,3,4,9-tetrahydro-1H-carbazole-4-carboxylic acid ethyl ester

HRID 1753933ノート

反応式

HRID 1753933 の反応式
[CH2:1]([O:8][CH2:9][CH2:10][NH:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:18]([O:20][C:21]([C:23]1[CH2:28][CH2:27][CH2:26][CH:25](Br)[C:24]=1O)=[O:22])[CH3:19]>CC(O)C.[Cl-].[Zn+2].[Cl-]>[CH2:18]([O:20][C:21]([CH:23]1[C:24]2[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[N:11]([CH2:10][CH2:9][O:8][CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[C:25]=2[CH2:26][CH2:27][CH2:28]1)=[O:22])[CH3:19]

参加物

5

反応物 2

HCID 571665N-Phenyl-2-benzyloxyethylamineHCID 590519613-Bromo-2-hydroxy-cyclohex-1-enecarboxylic acid ethyl ester

生成物 1

HCID 666793589-(2-Benzyloxy-ethyl)-2,3,4,9-tetrahydro-1H-carbazole-4-carboxylic acid ethyl ester収率 72%

試薬・触媒・溶媒 2

HCID 3007855Zincchloride触媒HCID 3776Isopropanol溶媒

反応条件

温度
50 °C

実験手順

A mixture of (2-benzyloxy-ethyl)-phenyl-amine (21; prepared according to Example 3(c)) (8.0 g, 26 mmol) and 3-bromo-2-hydroxy-cyclohex-1-enecarboxylic acid ethyl ester (4; prepared according to Example 1(d)) (3.2 g, 13 mmol) was stirred under N2 at 50° C. for 3 h and the reaction turned brown. The resulting mixture was dissolved in propan-2-ol (30 mL) and dry zinc chloride (10.6 g, 78 mmol) was added. The mixture was heated to reflux under N2 for 16 h and then concentrated in vacuo. The residue was dissolved in ethyl acetate (300 mL) and washed with 2 N HCl (100 mL), water (2×100 mL) and aqueous potassium carbonate solution (2×100 mL) then dried and concentrated in vacuo. The crude material was purified by silica gel chromatography eluting with petrol (A) and ethyl acetate (B) (2.5-40% B, 17 CV, 330 g, 100 mL/min) to give 3.49 g (72%) of 9-(2-benzyloxy-ethyl)-2,3,4,9-tetrahydro-1H-carbazole-4-carboxylic acid ethyl ester (25) as an oil. The structure was confirmed by 13C NMR (75 MHz, CDCl3) δC14.2, 20.5, 21.8, 26.5, 38.6, 42.9, 60.4, 68.7, 73.2, 106.4, 108.8, 118.7, 120.7, 127.4, 127.5, 128.3, 136.2, 136.9, 137.8, 175.0.

後処理

  1. temperatureThe mixture was heated
  2. temperatureto reflux under N2 for 16 h
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residue was dissolved in ethyl acetate (300 mL)
  5. washwashed with 2 N HCl (100 mL), water (2×100 mL) and aqueous potassium carbonate solution (2×100 mL)
  6. customthen dried
  7. concentrationconcentrated in vacuo
  8. customThe crude material was purified by silica gel chromatography
  9. washeluting with petrol (A) and ethyl acetate (B) (2.5-40% B, 17 CV, 330 g, 100 mL/min)

出典と根拠

ORDレコード
ord-c48e17a1c8cb4fee96220116b238e06e
出典データセット
uspto-grants-2015_10
特許番号
US09168317B2

反応ノート

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