研究生: |
鄭聖凡 |
---|---|
論文名稱: |
過錳酸鉀/鹽酸(氫溴酸)/氰甲烷試劑對羰基化合物及縮醛的鹵化研究 |
指導教授: | 劉高家秀 |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
畢業學年度: | 85 |
語文別: | 中文 |
論文頁數: | 87 |
中文關鍵詞: | 過錳酸鉀 、鹽酸 、氫溴酸 |
論文種類: | 學術論文 |
相關次數: | 點閱:125 下載:0 |
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利用過錳酸鉀的氰甲烷溶液與鹽酸搭配可形成一完全均相的墨綠色溶液,再加入10毫莫耳羰基受質,使過錳酸鉀/鹽酸/受質之毫莫耳數比等於 3:45:10 為試劑反應之比例,即可產生氯化反應。如為 β-酮基酯類 (β-ketoesters) 和1,3-雙酮類 (1,3-diketones) 等受質,在室溫(約20℃)下30分鐘之內,即完成氯化反應,生成相對應的α-位置單氯取代產物,產率為67-88%。而對於丙二酸二乙酯、具取代基的苯基甲基酮(p-Y-C6H4-COCH3, Y=H, Br, CH30) 則需將試劑加熱到60℃,反應可在3小時內完成,產率為28-86%。唯對其取代基苯基甲基酮除了單氯取代產物外還會有些許雙氯取代副產物,產率8-16%。
如欲進行溴化反應,則是將鹽酸改成氫溴酸,即可得均相之橙紅色試劑溶液;以過錳酸鉀/氫溴酸/受質之毫莫耳數比等於2:30:5 之比例反應,結果與氯化大致相同。對 β-酮基酯類與 1,3-雙酮類等活潑的化合物能在室溫 (20℃) 下30分鐘內完成反應,且只有得到α-位置單溴取代之羰基化合物,產率81-88%。至於丙二酸二乙酯、具取代基的苯基甲基酮 (p-Y-C6H4-COCH3, Y=H, Br, CH30) 需在60℃下反應,一樣可得到對應的單溴取代產物,產率56-87%。但具取代基之苯基甲酮會有少量雙溴取代產物,產率6-23%。
關於對縮醛部分的氯化及溴化,如依原步驟直接反應會生成α-鹵化醛類;但是將溶劑換成二氯甲烷,並加入四級銨鹽作相轉移,並在反應中作除水的步驟,以過錳酸鉀/四級銨鹽/鹽酸(氫溴酸)/受質之毫莫耳數比為 1.5:2:20:5,室溫 (20℃) 反應 3-6小時即可得到保護基不被破壞的α-氯(溴)取代縮醛產物,產率為60-81%。
Except for diethyl malonate and substituted acetophenones (p-Y-C6H4COCH3, Y=H, Br, CH30), simple ketones, β-ketoesters and 1,3-diketones reacted smoothly with a preformed homogeneous mixture of hydrochloric acid and potassium permanganate in acetonitrile to give moderate to good yields of the corresponding α-chlorocarbonyl compounds. Using a molar ratio of KMnO4:HCl:substrate of 3:45:10, chlorination was completed within thirty minutes at room temperature (ca. 20℃) to give α-chlorosubstituted β-ketoesters and 1,3-diketones in good yields (67-88%). When heated to 60℃, chlorination of diethyl malonate and substituted acetophenones (p-Y-C6H4COCH3, Y=H, Br, CH3O) yielded α-chlorosubstituted products in yields of 28% to 86%. But acetophenones gave 8-16% of α,α-dichlorocarbonyl compounds as the by-products.
Brominations of β-ketoesters and 1,3-diketones proceeded similarly and gave higher yields (81-88%), when the molar ratio of KMnO4:HBr:substrate was 2:30:5. Bromination of diethyl malonate and substituted acetophenones (p-Y-C6H4COCH3, Y=H, Br, CH3O) required heating the reaction mixture to 60℃, gave α- monosubstituted products in yields of 56% to 87%. However, there were 6-23% of α,α-dibromoacetophenones presented as the by-products.
By replacing acetonitrile with dichloromethane, and addition of tetraethylammonium salt as phase transfer agent, and removed water during reaction, acetals could be transferred to the corresponding α-chloro- or α-bromo- acetals in 60% to 81% yield.