Реакция #316392

Уравнение реакции

(4-bromophenyl)(3-chloro-4-hydroxyphenyl)methanone

(4-Bromophenyl)(3-chloro-4-hydroxyphenyl)methanone

cycloheptanone

K2CO3

→

compound 124

Выход 64.0%

4-[(4-Bromophenyl)(cycloheptylidene)methyl]-2-chlorophenol

Выход 64.0%

Растворители

THF

THF

Условия реакции

Обработка

1. 1
   Другоеat room temperature
2. 2
   ТемператураThe mixture was heated
3. 3
   Температураat reflux for 2 h
4. 4
   ТемператураThe reaction mixture was heated
5. 5
   Температураat reflux
6. 6
   ФильтрацияThe reaction mixture was filtered through a pad of Celite
7. 7
   Промывкаthe pad was washed with EtOAc (100 mL)
8. 8
   ДругоеThe filtrate was transferred to a separatory funnel
9. 9
   Другоеthe layers were separated
10. 10
    ЭкстракцияThe aqueous layer was further extracted with EtOAc (50 mL)
11. 11
    ПромывкаThe combined organic phase was washed with brine
12. 12
    Сушкаdried over Na2SO4
13. 13
    Фильтрацияfiltered
14. 14
    Концентрированиеthe filtrate was concentrated
15. 15
    Другоеto give the crude product as brown oil
16. 16
    ДругоеThe crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (20:1)

Методика

To a stirred suspension of zinc powder (1.35 g, 20.5 mmol) in THF (40 mL) was slowly added TiCl4 (1.13 mL, 10.3 mmol) via syringe at room temperature under a nitrogen atmosphere. The mixture was heated at reflux for 2 h. A solution of (4-bromophenyl)(3-chloro-4-hydroxyphenyl)methanone (105) (0.80 g, 2.57 mmol) and cycloheptanone (0.89 g, 7.70 mmol) in THF (15 mL) was added to the mixture. The reaction mixture was heated at reflux with stirring under a nitrogen atmosphere for 1.5 h. The reaction mixture was allowed to cool to room temperature. To the reaction mixture was slowly added 10% aqueous K2CO3 (40 mL). The reaction mixture was filtered through a pad of Celite and the pad was washed with EtOAc (100 mL). The filtrate was transferred to a separatory funnel and the layers were separated. The aqueous layer was further extracted with EtOAc (50 mL). The combined organic phase was washed with brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as brown oil. The crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (20:1) to give 0.64 g (64%) of compound 124 as a yellow viscous oil. 1H NMR (400 MHz, DMSO-d6): δ 1.50 (br s, 8H), 2.10-2.25 (m, 4H), 6.85-6.92 (m, 2H), 7.02 (br s, 1H), 7.07 (d, J=8.4 Hz, 2H), 7.47 (d, J=8.4 Hz, 2H), 10.1 (s, 1H). LCMS (APCI): m/z 413 (M+Na)+.

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