Реакция #1716782

Уравнение реакции

(2-benzyloxy-ethyl)-phenyl-amine

(2-Benzyloxy-ethyl)-phenyl-amine

3-bromo-2-hydroxy-cyclohex-1-enecarboxylic acid ethyl ester

3-Bromo-2-hydroxy-cyclohex-1-enecarboxylic acid ethyl ester

→

9-(2-benzyloxy-ethyl)-2,3,4,9-tetrahydro-1H-carbazole-4-carboxylic acid ethyl ester

Выход 72.0%

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

Выход 72.0%

Растворители

propan-2-ol

Условия реакции

Обработка

1. 1
   ТемператураThe mixture was heated
2. 2
   Температураto reflux under N2 for 16 h
3. 3
   Концентрированиеconcentrated in vacuo
4. 4
   workup.DISSOLUTIONThe residue was dissolved in ethyl acetate (300 mL)
5. 5
   Промывкаwashed with 2 N HCl (100 mL), water (2×100 mL) and aqueous potassium carbonate solution (2×100 mL)
6. 6
   Другоеthen dried
7. 7
   Концентрированиеconcentrated in vacuo
8. 8
   ДругоеThe crude material was purified by silica gel chromatography
9. 9
   Промывкаeluting with petrol (A) and ethyl acetate (B) (2.5-40% B, 17 CV, 330 g, 100 mL/min)

Методика

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) δC 14.2, 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.

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