反応 #2360769

反応方程式

1,8-dichloroanthraquinone

NH3

→

1,8-dichloroanthracene

収率 62.0%

反応条件

後処理

1. 1
   温度After cooling to room temperature
2. 2
   その他the resulting solid was separated by suction filtration
3. 3
   抽出extract of the supernatant liquid
4. 4
   乾燥the mixture was dried over MgSO4
5. 5
   濃縮concentrated under vacuo
6. 6
   workup.DISSOLUTIONThe residual crude solid was dissolved in a mixture of 500 ml of isopropanol and 50 ml of 12 M HCl
7. 7
   温度After the resulting solution had been refluxed for 3 h
8. 8
   濃縮it was concentrated
9. 9
   その他partitioned between CH2Cl2 and 5% NaHCO3
10. 10
    その他The organic layer was collected
11. 11
    乾燥dried over MgSO4
12. 12
    その他The solvent was evaporated
13. 13
    その他the crude solid product was recrystallized from a CH2Cl2-hexane mixture
14. 14
    その他to dry in the air for 24 h

実験手順

A suspension of 1,8-dichloroanthraquinone 1 (10.0 g, 36.1 mmol) and Zinc dust (50.0 g, 765 mmol) in 200 ml of aqueous 28% NH3 was stirred for 3 h at 100° C. After cooling to room temperature, the resulting solid was separated by suction filtration. A CH2Cl2 solution of the resulting crude solid was combined with the CH2Cl2 extract of the supernatant liquid, and the mixture was dried over MgSO4 and concentrated under vacuo. The residual crude solid was dissolved in a mixture of 500 ml of isopropanol and 50 ml of 12 M HCl. After the resulting solution had been refluxed for 3 h, it was concentrated and partitioned between CH2Cl2 and 5% NaHCO3. The organic layer was collected and dried over MgSO4. The solvent was evaporated, and the crude solid product was recrystallized from a CH2Cl2-hexane mixture. The collected product was allowed to dry in the air for 24 h to provide 5.5 g (62%) of 1,8-dichloroanthracene 2 as yellow needles: mp 153° C. IR (KBr): ν=1617, 1547, 1438, 1300, 1210, 953, 872, 775, 720, 678; 1H NMR (CDCl3, 400 MHz) δ=7.25-7.88 (m; 6H, ArH), 8.36 (s; 1H, ArH-10), 9.16 (s; 1H, ArH-9); 13C NMR (CDCl3, 400 MHz) δ=120.99, 125.68, 126.04, 127.33, 127.61, 132.63; MS (EI) m/z (%)=246 (100) [M+], 248 (65); HRMS (EI) Calcd. For C14H8Cl2 [M+] 246.0003, Found 246.0001.

出典