反応 #3860

反応方程式

carbonate

potassium carbonate

1,4-dioxane

(Z,Z)-11,13-hexadecadienal

→

(Z,Z)-1,12,14-heptadecatriene

溶媒

water

反応条件

後処理

1. 1
   その他was prepared in a 100 ml round bottomed flask
2. 2
   その他equipped with a magnetic stirrer
3. 3
   温度thermometer and reflux condenser
4. 4
   温度The mixture was heated
5. 5
   温度to reflux at 105°-110°
6. 6
   その他were withdrawn periodically
7. 7
   その他partitioned between 1 ml of H2O and 1 ml of hexane
8. 8
   その他at 1.1 and 2.2 and 17 hr
9. 9
   workup.ADDITIONMore potassium carbonate (1.7 g) was added at 212 hr
10. 10
    その他the reaction to completion
11. 11
    温度The reaction mixture was cooled
12. 12
    抽出extracted 3 times with 25 ml of hexane
13. 13
    抽出the organic layer was extracted with water
14. 14
    その他dried
15. 15
    その他the solvent removed

実験手順

(Z,Z)-1,12,14-heptadecatriene (TRIENE) was synthesized conveniently from Wittig Salt and aldehyde in aqueous dioxidepotassium carbonate heterogeneous medium (Lechat 1982). A mixture of 3.57 g (0.01 mol) of methyl triphenylphosphonium bromide (Alfa Inorganics), 1.7 g (0.14 mol) of potassium carbonate, 10 ml of 1,4-dioxane, 0.15 ml of water and 2.36 g (0.01 mol) of (Z,Z)-11,13-hexadecadienal (AL. Albany International) was prepared in a 100 ml round bottomed flask equipped with a magnetic stirrer, thermometer and reflux condenser. The mixture was heated to reflux at 105°-110° with stirring while aliquots of 15 ul were withdrawn periodically and partitioned between 1 ml of H2O and 1 ml of hexane. Analysis by gas-liquid chromatography, showed 66, 70 and 99% triolefin and 30%, 26% and 1% starting aldehyde at 1.1 and 2.2 and 17 hr, respectively. More potassium carbonate (1.7 g) was added at 212 hr to drive the reaction to completion. The reaction mixture was cooled and extracted 3 times with 25 ml of hexane, then the organic layer was extracted with water, dried and the solvent removed to leave 1.8 g of yellow oil and a few crystals of triphenylphosphine oxide. The oil was taken up in hexane and passed through a 1×45 cm column of silica gel (60-200 mesh, Baker) with hexane, to yield 1.7 g (73% yield) of clear oil.

出典