Реакция #2275682

Уравнение реакции

1-(2-clorophenyl)-3-methylisoquinoline

1-(2-chlorophenyl)-3-methylisoquinoline

N-bromo-succinimide

benzoyl peroxide

1-(2-clorophenyl)-3-isoquinolinecarboxylic acid

→

1-(2-clorophenyl)-3-isoquinolinecarboxaldehyde

Растворители

CCl4

Условия реакции

Обработка

1. 1
   Температураwas heated
2. 2
   Температураto reflux
3. 3
   Другоеwhile being illuminated by a flood lamp for 5 hours
4. 4
   Фильтрацияfiltered
5. 5
   ПромывкаThe filtrate was washed with saturated NaHCO3 (1×40 mL)
6. 6
   Сушкаdried with Na3SO4
7. 7
   Фильтрацияfiltered
8. 8
   Концентрированиеconcentrated in vacuo
9. 9
   workup.ADDITION(10.13 g) in EtOH (140 mL) and THF (70 mL) was added dropwise a solution of AgNO3 (10.595 g) in H2O (6 mL)
10. 10
    ТемператураThe mixture was refluxed for 1 hour
11. 11
    Фильтрацияfiltered hot
12. 12
    ПромывкаThe filter cake was washed with hot THF (2×20)
13. 13
    КонцентрированиеThe combined filtrate was concentrated in vacuo

Методика

Then 1-(2-clorophenyl)-3-isoquinolinecarboxylic acid 81 is formed by the following process. A mixture of 1-(2-clorophenyl)-3-methylisoquinoline 77 (6.68 g, 19.88 mmol), N-bromo-succinimide (NBS) (8.896 g, 19.98 mmol), and benzoyl peroxide (BPO) (0.57 g) in CCl4 was heated to reflux while being illuminated by a flood lamp for 5 hours. The reaction was cooled to room temperature and filtered. The filtrate was washed with saturated NaHCO3 (1×40 mL), dried with Na3SO4, filtered and concentrated in vacuo. The crude dibromide yellow product 79 was used in the next step. To a refluxing solution of the crude dibromide 79. (10.13 g) in EtOH (140 mL) and THF (70 mL) was added dropwise a solution of AgNO3 (10.595 g) in H2O (6 mL). The mixture was refluxed for 1 hour and filtered hot. The filter cake was washed with hot THF (2×20). The combined filtrate was concentrated in vacuo to give crude 1-(2-clorophenyl)-3-isoquinolinecarboxaldehyde as a dark yellow oil. (9 g) This oil was used without purification. To a solution of the crude aldehyde in absolute EtOH (100 mL) was slowly added a solution of AgNO3 (11.11 g) in 10 mL H2O. to this stirred solution was added dropwise a solution of NaOH (9.43 g) in H2O (140 mL). The resulting black slurry was stirred at room temperature for 2 hours. The solution was then filtered through a Celite column. The filter cake was washed with ether. The ether was evaporated and the aqueous solution was made slightly acidic with concentrated HCl. The precipitate was collected by filtration, then washed with H2O. It was then recrystallized from CH3CN affording pale yellow crystals (2.63 g, 35%).

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