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系統識別號 U0002-2402201414094600
中文論文名稱 一鍋化型式的巴比艾爾及氧化反應合成丙炔基酮與丙炔基醇
英文論文名稱 One-pot Synthesis of Propargylic Alcohol and Ketone via Barbier Reaction and Oxidation
校院名稱 淡江大學
系所名稱(中) 化學學系碩士班
系所名稱(英) Department of Chemistry
學年度 102
學期 2
出版年 103
研究生中文姓名 吳鐵綱
研究生英文姓名 Tieh-Kang Wu
電子信箱 dennisyyyyy@hotmail.com
學號 600160120
學位類別 碩士
語文別 中文
口試日期 2014-01-17
論文頁數 80頁
口試委員 指導教授-李世元
委員-王伯昌
委員-陳錦地
中文關鍵字 一鍋化  巴比艾爾  氧化  丙炔基酮  丙炔基醇 
英文關鍵字 Propargylic Ketone  Propargylic Alcohol  One-pot  Barbier Reaction  Acetylenic Ketone  Oxidation 
學科別分類 學科別自然科學化學
中文摘要 丙炔基酮類化合物可以用做抗菌抗黴劑添加在化妝品與食品當中,以防止微生物繁殖造成的腐敗與變質。而過去的丙炔基酮化合物合成方法多透過氧化丙炔基醇製備,但此方法需要先合成丙炔基醇,所以需要兩步驟合成丙炔基酮。而另一種合成方式以醯基鹵化物為起始物可一步合成丙炔基酮,但醯基鹵化物多數不穩定且難予製備。為了改善過去合成丙炔基酮的不便之處,本論文提出以一鍋化的巴比艾爾反應與氧化反應合成丙炔基酮,不但步驟簡化,且起始物為穩定的醛類化合物。本論文用醛類化合物為起始物,將其加入在超音波促進巴比艾爾反應中以鎂金屬及溴苯形成格林納試劑去質子化的苯乙炔反應,再加入氧化劑PCC後便可得到丙炔基酮化合物。
英文摘要 Propargylic Ketone derivatives were employed as antiseptic in cosmeticians and foods. Many synthetic methods for preparation of propargylic ketone have been reported. Among these reported methods, the common used method was deprotonation of terminal alkyne and then reacted with aldehyde, further oxidation of propargylic alcohol to afford propargylic alcohol. A direct method was terminal alkyne which was reacted with acyl halide by introducing transition metal as catalyst.
This paper presented a new method of one-pot systhesis of propargylic ketone from Aldehyde. We can obtain propargylic ketone in one-pot reaction by reaction of the aldehyde with deprotonated phenylacetylene via Barbier reaction and then a PCC was added to the reaction mixture.
論文目次 目錄
中文摘要 I
英文摘要 II
圖表目錄 III
光譜目錄 IV

第一章 序論…………………………………………………………1
1-1 抗菌抗黴劑的分類…………………………………………5
(1) 藥物性抗菌抗黴劑的起源發展與應用……………………5
(2) 非藥物性抗菌抗黴劑的起源發展與應用…………………8
1-2 丙炔基酮類化合物的化學合成方法………………………11
(1) 丙炔基醇的合成方法………………………………………12
(2) 經由氧化丙炔基醇製備丙炔基酮…………………………16
(3) 以醯基鹵化物為起始物之丙炔基酮合成方法……………21
(4) 特殊的丙炔基酮合成方法…………………………………22
1-3 丙炔基類化合物的應用……………………………………24

第二章 結果與討論…………………………………………………27
2-1 超音波在有機合成上的應用…………………………………27
(1) 超音波的物理與化學現象………………………………………27
(2)一般實驗室使用的超音波………………………………………29
2-2 反應條件與結果………………………………………………32

第三章 實驗與儀器…………………………………………………44
3-1 實驗方法…………………………………………………………44
3-2溶劑的乾燥………………………………………………………48
3-3 實驗儀器與測試方法……………………………………………49

第四章 總結…………………………………………………………51

第五章 光譜…………………………………………………………53

第六章 參考資料……………………………………………………77


圖表目錄
Scheme 1-1 Oxidation of Propargylic Alcohol to Ketone ……2
Scheme 1-2 Synthesis of Propargylic Alcohols via
Sonochemical Barbier Reaction ……………………………………4
Scheme 1-3 Structure of Penicillin and Sulfonamide…………6
Scheme 1-4 Synthesis of Propargylic Ketone……………………11
Scheme 1-5 Mechanism of Propargylic Alcohol Synthesis ……12
Scheme 1-6 Examples of Propargylic Alcohol Synthesis by n-Butyllithium…………………………………………………………13
Scheme 1-7 Examples of Propargylic Alcohol Synthesis
by Ethylmagnesium Bromide …………………………………………14
Scheme 1-8 Examples of Propargylic Alcohol Synthesis by Diethylzinc ……………………………………………………………15
Scheme 1-9 Oxidants PCC and PDC …………………………………16
Scheme 1-10 Examples of Propargylic Alcohol Oxidation by
Manganese dioxide ……………………………………………………17
Scheme 1-11 Oxidation Mechanism of
Primary Alcohol to Aldehyde by PCC………………………………18
Scheme 1-12 Examples of Propargylic Alcohol Oxidation by
Chromium Derived Oxidants …………………………………………19
Scheme 1-13 Martin’s Reagent (DMP) ……………………………19
Scheme 1-14 Examples of Propargylic Alcohol Oxidation by
Martin’s Reagent ……………………………………………………20
Scheme 1-15 Synthesize Propargylic Ketone form Acyl Chloride…………………………………………………………………21
Scheme 1-16 Mechanism of Propargylic Ketone Preparation by Vanadium Trichloride…………………………………………………22
Scheme 1-17 Preparation of Propargylic Ketone by Indium …23
Scheme 1-18 Top of Line Corrosion – Gate ……………………25
Scheme 2-1 Ultrasonic Cleaner ……………………………………30
Scheme 2-2 Lithium involved Sonochemical Barbier-type Reaction…………………………………………………………………30
Scheme 2-3 Lithium with CuI involved Sonochemical
Barbier-type Reaction………………………………………………30
Scheme 2-4 Organostannane Synthesis via
Sonochemical Barbier Reaction ……………………………………31
Scheme 2-5 Unsymmetric Ketone Synthesis via
Sonochemical Barbier Reaction and Oxidation …………………31
Scheme 2-6 Retro-synthesis of Propargylic Ketone……………32
Scheme 2-7 Formation of Propargylic Alcohol Intermediate ……………………………………………………………………………33
Scheme 2-8 Yield of One-pot Synthesis of Propargylic Ketone ……………………………………………………………………………38


Table 1 …………………………………………………………………34
Table 2 …………………………………………………………………36
Table 3 …………………………………………………………………37
Table 4 …………………………………………………………………39
Table 5 …………………………………………………………………42


光譜目錄

Part 1 : Propargylic Ketone Derivatives
3-phenyl-1-(p-tolyl)prop-2-yn-1-one (1H-NMR,13C-NMR)
1-(benzo[d][1,3]dioxol-5-yl)-3-phenylprop-2-yn-1-one (1H-NMR, 13C-NMR)
1-(4-(methylthio)phenyl)-3-phenylprop-2-yn-1-one (1H-NMR, 13C-NMR, IR, Mass)
1-(4-fluorophenyl)-3-phenylprop-2-yn-1-one (1H-NMR, 13C-NMR)
3-phenyl-1-(thiophen-2-yl)prop-2-yn-1-one (1H-NMR, 13C-NMR)
1-(furan-2-yl)-3-phenylprop-2-yn-1-one (1H-NMR, 13C-NMR)
3-phenyl-1-(pyridin-3-yl)prop-2-yn-1-one (1H-NMR,13C-NMR)
1-(naphthalen-1-yl)-3-phenylprop-2-yn-1-one (1H-NMR, 13C-NMR)
1-phenyloct-1-yn-3-one (1H-NMR,13C-NMR)
(E)-1-phenyloct-4-en-1-yn-3-one (1H-NMR, 13C-NMR, IR, Mass)
1-cyclohexyl-3-phenylprop-2-yn-1-one (1H-NMR, 13C-NMR)

Part 2 : Propargylic Alcohol Derivatives
3-phenyl-1-(p-tolyl)prop-2-yn-1-ol (1H-NMR,13C-NMR)
1-(benzo[d][1,3]dioxol-5-yl)-3-phenylprop-2-yn-1-ol (1H-NMR,13C-NMR)
1-(4-(methylthio)phenyl)-3-phenylprop-2-yn-1-ol (1H-NMR, 13C-NMR, IR, Mass)
1-(4-fluorophenyl)-3-phenylprop-2-yn-1-ol (1H-NMR,13C-NMR)
1-(4-nitrophenyl)-3-phenylprop-2-yn-1-ol (1H-NMR,13C-NMR)
3-phenyl-1-(thiophen-2-yl)prop-2-yn-1-ol (1H-NMR,13C-NMR)
1-(furan-2-yl)-3-phenylprop-2-yn-1-ol (1H-NMR,13C-NMR)
3-phenyl-1-(pyridin-3-yl)prop-2-yn-1-ol (1H-NMR,13C-NMR)
1-(naphthalen-1-yl)-3-phenylprop-2-yn-1-ol (1H-NMR,13C-NMR)
1-phenyloct-1-yn-3-ol (1H-NMR,13C-NMR)
(E)-1-phenyloct-4-en-1-yn-3-ol (1H-NMR, 13C-NMR, IR, Mass)
1-cyclohexyl-3-phenylprop-2-yn-1-ol (1H-NMR,13C-NMR)

1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one (1H-NMR,13C-NMR)
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