本論文使用七種苯醌化合物，分別在DMF及MeCN溶劑中與醇類及酸作用，以0.1M六氟磷酸四丁基銨鹽當做電解質，利用循環伏安法偵測，可以得到苯醌化合物第二段氧化還原波往正電位方向偏移，經由加入不同濃度醇類所造成的結果，以電位對濃度作圖的斜率，其大小可以反映出作用的程度。由實驗結果獲知醇類反應性趨勢：甲醇＞乙醇＞丙醇＞丁醇≧異丙醇。 苯醌化合物兩個氧化還原波在形成陰離子及雙陰離子時，由CV圖上得到第二段電位往正方向偏移時，其可逆形式幾乎沒有改變，氧化還原電流高度比也接近常數值。當添加物為醇時，其pKa越小時，則第二段氧化還原波往正偏移就越大。當添加物為改為酸時，其酸性越大時，則第二段氧化還原波峰就幾乎是不可逆的，這主要是由於作用太快，因此還未測定就產生反應了。 利用Hammett方程式來探討苯醌化合物的取代效應，發現七個苯醌化合物中所有取代基為推電子基時，其σ值皆為負值。 苯醌化合物在非水溶液中與一系列醇的化學作用，提出其反應機構為 這在電化學中是屬ECE反應機構，本實驗結果可以支持自由基的反應機構。 Abstract Hydrogen-bonding, acidity, and structural variation are major factors controlling potentials and mechanisms in the reduction of seven quinones. These are investigated systematically in dimethylforamide and acetonitrile solutions by cyclic voltammetry for a series of quinones with increasing basicity, and in the presence of hydroxylic additives of increasing hydrogen-bonding power or acidity. Redox effects are demonstrated over the complete interaction range, hydrogen bonding of reduced dianions to protonation of unreduced quinones. It is found that the interactions of these systems decrease in the order MeOH>EtOH>n-PrOH>n-BuOH≧i-PrOH for alcohol additives. Two well-separated reduction waves, corresponding to the formation of quinone mono- and dianion, shift positively, with no loss of reversibility. The relative height of the wave remains constant. The pKa values are less, the second wave shift more positively. When reaction change to use acid as additives, the more acid, the second wave is almost irreversible. This should be too fast to measure. Using Hammett equation to understand quinones about substituent effects, we find that seven quinones are electron-donating group. The σvalues are all negative. As a result, these quinones are interacting with a series alcohols and acids which can propose the reaction mechanism in aprotic solvent as These results should be a major reaction mechanism of the electrochemistry and are supported radical reaction mechanism.
