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研究生:黃君平
研究生(外文):Chung-Ping Huang
論文名稱:利用相間轉移觸媒氧化丁基硫醚與其應用之研究
論文名稱(外文):Study of the Oxidation of Dibutyl Sulfide by Phase Transfer Catalysis and Its Applications
指導教授:王茂齡
指導教授(外文):Maw-Ling Wang
學位類別:碩士
校院名稱:東海大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
論文頁數:208
中文關鍵詞:相間轉移觸媒氧化硫醚丁基硫醚
外文關鍵詞:phase transfer catalysisOxidation of thioetherdibutyl sulfide
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本論文之研究主要是利用相間轉移觸媒進行硫醚化合物之氧化反應,硫醚化合物之氧化產物為sulfoxide與sulfone,此兩種化合物之用途皆為十分廣泛之藥物中間體,可作為有機反應之中間物。本論文乃欲利用價廉且低污染之氧化劑-次氯酸鈉作為氧化劑,以四級銨鹽做為相間轉移觸媒對正二丁基硫醚進行單氧化及雙氧化反應。相間轉移觸媒可與水溶性氧化劑結合為活性中間體,形成油溶性之氧化劑,故可改善傳統氧化方法的缺點:昂貴(有機氧化劑)、污染性(鉻酸、錳酸、硝酸等氧化劑)、不易分離(共溶劑)與高溫操作條件。而其中次氯酸鈉可直接與相間轉移觸媒直接形成具有氧化力之活性觸媒,而過氧化氫則需另外加入助觸媒,故選用本文次氯酸鈉為氧化劑。本論文的內容研究重點為:(a)兩相系統之反應機構(b)動力學模式推導(c)一次與二次氧化速率常數(k1與k2)、活化能、速率決定步驟之求得(d)動力學行為及不同操作條件對反應之影響(e)強鹼性次氯酸鈉水溶液與觸媒之結合能力(f)次氯酸鈉之濃度及pH值對反應的影響(g)氧化劑次氯酸鈉在哪些條件下具有氧化選擇性(即僅生成單氧化產物或雙氧化產物)等方面。
本論文較特殊之處,是討論強鹼性次氯酸鈉水溶液與相間轉移觸媒之離子交換關係,改善次氯酸鈉在強鹼環境下不佳的反應效果,並使用不同濃度之次氯酸鈉水溶液對反應系統之影響作深入的探討。
The primary objective of this dissertation is to study the oxidation of thioethers by phase transfer catalysis. The oxidation derivatives of the thioethers are sulfoxide and sulfone, which are widely applied as the intermediates of medicines and organic chemicals. In this dissertation, we carried out the oxidization of n-dibutyl sulfide by sodium hypochlorite which is inexpensive and low pollution to synthesize mono-oxidation and di-oxidation products using quaternary ammonium salts as phase transfer catalyst. The mono-oxidation and di-oxidation products of dibutyl sulfide are dibutyl sulfoxide and dibutyl sulfone, respectively. The phase transfer catalyst reacts with sodium hypochlorite to form organophilic oxidant (active catalyst), so the disadvantages of traditional method of heterogeneous oxidation, such as expensive oxidant (organophilic oxidant), polluted (chromic, manganic and nitric acid), unseparated (co solvent), and high reaction temperature are avoided. The key of this dissertation are: (a) proposing the mechanism of two phase reaction; (b) deriving of the kinetic model; (c) determining of the 1st and 2nd rate constant, activation energy and rate determine step; (d) searching kinetics and operating factors which affect the reactions and product yields; (e) finding the oxidation ability of sodium hypochlorite under strong alkalinity; (f) investigating the concentration of sodium hypochlorite and pH value which affect the reactions; (g) examining the selectivity of oxidant sodium hypochlorite.
In this work, the ionic exchange between sodium hypochlorite and phase transfer catalyst under strong alkalinity and how to improve the reaction rate were discussed. Different concentrations of sodium hypochlorite which possesses oxidation capability in affecting the reactions were investigated in detail.
中文摘要……………………………………………………………… Ⅰ
英文摘要……………………………………………………………… Ⅱ
誌謝…………………………………………………………………… Ⅲ
目錄…………………………………………………………………… Ⅳ
表目錄………………………………………………………………… Ⅶ
圖目錄………………………………………………………………… Ⅸ
符號說明…………………………………………………………… ⅩⅤⅢ
第一章 緒論……………………………………………………… 1
§1.1 前言…………………………………………………… 1
§1.2 相間轉移觸媒之發展歷史…………………………… 3
§1.3相間轉移觸媒之分類………………………………… 6
§1.4相間轉移觸媒催化反應機構………………………… 14
§1.4.1依反應發生的位置分類……………………… 14
§1.4.2 依觸媒轉移的途徑分類……………………… 17
§1.5觸媒的回收和分離方面……………………………… 18
§1.6研究動機及目的……………………………………… 21
§1.7文獻回顧……………………………………………… 22
第二章 實驗之藥品與儀器設備………………………………… 25
§2.1實驗藥品……………………………………………… 25
§2.2 實驗設備……………………………………………… 26
§2.3 分析儀器……………………………………………… 27
第三章 實驗方法與步驟………………………………………… 30
§3.1 正二丁硫醚氧化產物之合成………………………… 30
§3.2 產物的純化…………………………………………… 30
§3.3 產物之鑑定…………………………………………… 31
§3.4 動力學實驗…………………………………………… 35
§3.5 有機化合物之校正曲線……………………………… 40
第四章 正二丁基硫醚與次氯酸鈉的氧化反應………………… 46
§4.1正二丁基硫醚與次氯酸鈉氧化反應機構…………… 46
§4.2 反應機構之數理模式………………………………… 47
§4.3 實驗結果與討論……………………………………… 52
§4.3-1 攪拌速率之影響……………………………… 52
§4.3-2 觸媒用量對反應速率的影響………………… 59
§4.3-3 溫度對反應速率之影響……………………… 66
§4.3-4 觸媒種類的影響……………………………… 73
§4.3-5 有機相體積對反應速率的影響……………… 80
§4.3-6 水量對反應之影響…………………………… 88
§4.3-7 加入酸性物質對反應的影響………………… 95
§4.3-8 不同量之碳酸氫鈉對反應的影響…………… 102
§4.3-9 外加不同無機鹽類對反應的影響…………… 109
§4.3-10 不同有機溶劑對反應的影響……………… 116
第五章 高濃度次氯酸鈉氧化正二丁基硫醚之反應………… 129
§5.1 前言………………………………………………… 129
§5.2 反應速率式推導…………………………………… 130
§5.3 實驗結果與討論…………………………………… 131
§5.3-1 12%次氯酸鈉25 ml對反應的影響………… 132
§5.3-2 加5 ml去離子水並取20 ml次氯酸鈉對反
應的影響…………………………………… 141
§5.3-3 加10ml去離子水並取15 ml次氯酸鈉對反
應的影響…………………………………… 149
§5.3-4 加15 ml去離子水並取10 ml次氯酸鈉對反
應的影響……………………………………… 156
§5.3-5 不同有機溶劑加入微量觸媒對反應的影響… 163
§5.3-6 不同有機溶劑在未添加觸媒情況下對反應的
影響…………………………………………… 169
§5.3-7 有機相體積對反應的影響…………………… 175
§5.3-8 溫度對反應速率之影響……………………… 183
§5.3-9 加入醋酸降低pH值對反應的影響………… 190
第六章 結論與展望
§6.1 結論…………………………………………………… 198
§6.2 展望…………………………………………………… 202
參考文獻………………………………………………………… 203
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