反応 #1830526

反応方程式

lithium hydroxide

2,4-dihydroxyacetophenone

9-fluorenone-4-carbonyl chloride

HCl

→

2-(9-fluorenon-4-yl)hydroxychromone

溶媒

THF

THF

反応条件

後処理

1. 1
   その他Dry
2. 2
   温度After the mixture has been re-cooled to −78° C.
3. 3
   workup.STIRRINGThe mixture is stirred at −78° C. for one hour and at room temperature for 4 hours until the starting material
4. 4
   抽出extracted with chloroform (3×50 ml)
5. 5
   その他The solvents are removed from the dried extracts
6. 6
   その他the residue is dried under reduced pressure for 24 hours
7. 7
   workup.ADDITIONGlacial acetic acid (30 ml) and sulfuric acid (0.2 ml) are added to the residue
8. 8
   温度the mixture is heated at 95–100° C. for from 30 minutes to one hour under an argon atmosphere
9. 9
   ろ過The precipitated product is filtered
10. 10
    洗浄washed
11. 11
    その他dried
12. 12
    その他recrystallised in methanol

実験手順

Dry, pulverulent lithium hydroxide (11.55 mmol, 3.3 equivalents) is added in one portion to a well-stirred solution of 2,4-dihydroxyacetophenone (3.22 mmol) in dry THF (5 ml) under an argon atmosphere at −78° C. The reaction mixture is stirred at −78° C. for one hour and subsequently at −10° C. for two hours. After the mixture has been re-cooled to −78° C., a solution of 9-fluorenone-4-carbonyl chloride (3.3 mmol) in THF (10 ml) is added in one portion. The mixture is stirred at −78° C. for one hour and at room temperature for 4 hours until the starting material has disappeared. The reaction mixture is emptied into a mixture of ice (150 g) and concentrated HCl (5 ml) and extracted with chloroform (3×50 ml). The solvents are removed from the dried extracts, and the residue is dried under reduced pressure for 24 hours. Glacial acetic acid (30 ml) and sulfuric acid (0.2 ml) are added to the residue, and the mixture is heated at 95–100° C. for from 30 minutes to one hour under an argon atmosphere. Approximately one third of the acetic acid is stripped off, and the residue is emptied into water. The precipitated product is filtered, washed and dried and recrystallised in methanol, giving 2-(9-fluorenon-4-yl)hydroxychromone. EI-MS (70 eV) m/e (rel. abund.)=340.

出典