反応 #10574

反応方程式

3

4-Tetrahydropyranyloxyphenylacetylene

4-bromobenzotriflouride

→

4-Tetrahydropyranyloxy-4′-trifluormethyltolan

溶媒

diisopropylamine

反応条件

後処理

1. 1
   その他the solution was degassed
2. 2
   温度cooled to room temperature
3. 3
   その他The salt formed during the reaction procedure
4. 4
   ろ過was filtered off
5. 5
   洗浄washed well with ethyl acetate
6. 6
   その他The filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (10 ml), water (100 ml)
7. 7
   その他crushed ice (50 g)
8. 8
   抽出extracted with ethyl acetate
9. 9
   洗浄The combined organic paste was washed with brine
10. 10
    乾燥dried over MgSO4
11. 11
    その他The solvent was removed in vacuo
12. 12
    その他the residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1)
13. 13
    その他to give a pale yellow crystals of 4

実験手順

A solution of 3 (12.1 g, 60 mmol) and 4-bromobenzotriflouride (14.85 g, 66 mmol) in diisopropylamine (250 ml) was heated to 30° C. under nitrogen, and the solution was degassed. Then Pd(PPh3)2Cl2 (210 mg, 0.3 mmol) and copper(I) iodide (114 mg, 0.6 mmol) were added to this clear solution. The reaction mixture was stirred for 2 hours at 80° C., then cooled to room temperature. The salt formed during the reaction procedure was filtered off and washed well with ethyl acetate. The filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (10 ml), water (100 ml) and crushed ice (50 g), then extracted with ethyl acetate. The combined organic paste was washed with brine and dried over MgSO4. The solvent was removed in vacuo and the residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1) to give a pale yellow crystals of 4. Yield 16.6 g (80%); mp 112˜113° C.; δH(CDCl3; 300 MHz): 7.59(s, 4H, Ar—H), 7.48(d, J=8.7, 2H, Ar—H), 7.04(d, J=8.7, 2H, Ar—H), 5.46(t, J=3.1, 1H, OCHO), 3.89(m, 1H, THP), 3.62(m, 1H, THP), 1.86˜1.62(m, 6H, THP).

出典