Реакция #316315

Уравнение реакции

cycloheptanone

(4-bromophenyl)(4-hydroxyphenyl)methanone

(4-Bromophenyl)(4-hydroxyphenyl)methanone

→

compound ( 9 )

Выход 71.0%

4-[(4-Bromophenyl)(cycloheptylidene)methyl]phenol

Выход 71.0%

Растворители

THF

THF

Условия реакции

Обработка

1. 1
   ДругоеTo a three-neck round-bottomed flask equipped with a magnetic stir bar
2. 2
   Температураreflux condenser
3. 3
   ТемператураThe reaction mixture was heated
4. 4
   Температураat reflux for 2 h
5. 5
   ДругоеTo the refluxing reaction mixture
6. 6
   ТемператураThe reaction mixture was heated
7. 7
   Температураat reflux under a nitrogen atmosphere
8. 8
   ДругоеThe oil bath was removed
9. 9
   ДругоеThe three neck round-bottomeded flask was equipped with an addition funnel
10. 10
    workup.ADDITIONwater (150 mL) was slowly added to the reaction mixture
11. 11
    ФильтрацияThe reaction mixture was filtered through a pad of Celite
12. 12
    ПромывкаThe pad was washed with EtOAc
13. 13
    ДругоеThe filtrate was transferred to a separatory funnel
14. 14
    Другоеthe layers were separated
15. 15
    ПромывкаThe organic phase was washed with brine
16. 16
    Сушкаdried over MgSO4
17. 17
    Фильтрацияfiltered
18. 18
    Концентрированиеthe filtrate was concentrated
19. 19
    Другоеto give the crude product as an orange oil
20. 20
    ДругоеThe crude product was partially purified
21. 21
    Другоеby flush chromatography on silica gel with hexanes:EtOAc (100:0 to 95:5)
22. 22
    Другоеto give a solid
23. 23
    ДругоеThe solid was triturated with hexanes
24. 24
    Фильтрацияfiltered

Методика

To a three-neck round-bottomed flask equipped with a magnetic stir bar, reflux condenser, rubber septum, and two nitrogen inlets, was added zinc powder (13.0 g, 199 mmol) followed by anhydrous THF (200 mL). To the stirred suspension was slowly added TiCl4 (11.0 mL, 19.0 g, 100.0 mmol) via syringe (caution: vigorous fuming). The reaction mixture was heated at reflux for 2 h. To the refluxing reaction mixture was added a solution of cycloheptanone (9.0 mL, 8.56 g, 76.3 mmol) and (4-bromophenyl)(4-hydroxyphenyl)methanone (2) (6.91 g, 24.9 mmol) in THF (200 mL) slowly via syringe. The reaction mixture was heated at reflux under a nitrogen atmosphere with stirring for 2 h. The oil bath was removed and the reaction mixture was allowed to cool to room temperature. The three neck round-bottomeded flask was equipped with an addition funnel and water (150 mL) was slowly added to the reaction mixture followed by 10% aqueous K2CO3 (150 mL). The reaction mixture was filtered through a pad of Celite. The pad was washed with EtOAc. The filtrate was transferred to a separatory funnel and the layers were separated. The organic phase was washed with brine, dried over MgSO4, filtered, and the filtrate was concentrated to give the crude product as an orange oil. The crude product was partially purified by flush chromatography on silica gel with hexanes:EtOAc (100:0 to 95:5) to give a solid. The solid was triturated with hexanes and filtered to give 6.3 g (71%) of compound (9) as an off-white solid. 1H NMR (400 MHz, DMSO-d6): δ 1.50 (m, 8H), 2.20 (m, 4H), 6.66 (d, J=8.5 Hz, 2H), 6.89 (d, J=8.4 Hz, 2H), 7.04 (d, J=8.4 Hz, 2H), 7.45 (d, J=8.4 Hz, 2H), 9.30 (s, 1H).

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