Abstract
本論文以氧化▊啶為反相間轉移觸媒, 進行苯甲醯氯與▊酸鹽類於水/二氯甲烷兩相中之取代反應研究. 其研究目標主要探討 (I)▊酸鹽效應,(II)雙▊酸鹽效應, (III)溶劑效應, (IV) 有機相氧化▊啶分佈效應,(V)氨基酸鹽效應, (VI)混合觸媒效應. 綜合結論如下: 1.轉速大於1100rpm, 反應速率與轉速無關. 2.適當條件下, 反應速率決定步驟發生於有機相氧化▊啶與苯甲醯氯形成中間物之步驟, 速率式為苯甲醯氯及氧化▊啶之一級反應. 3.無觸媒催化下, ▊酸根離子及雙▊酸根離子與苯甲醯氯反應慢, 主產物為苯甲酸. 4.氧化▊啶催化下, 苯甲醯氯與乙酸鈉在不同有機溶劑之反應活性次序為二氯甲烷 > 氯仿 > 四氯化碳. 5.氧化▊啶催化下, 乙酸, 丙酸, 異丁酸, 正戊酸, 正己酸, 正庚酸及正辛酸等單▊酸之離子與苯甲醯氯可快速產生主產物不對稱酸▊(PhCOOCOR).6.氧化▊啶催化下, 雙▊酸根離子與苯甲醯氯反應產物有苯甲酸,苯甲酸▊, 單取代酸▊(PhCOOCORCOOH)及雙取代酸▊, 其分佈與雙▊酸根離子有關. 草酸根,丙二酸根, 順-丁烯二酸根及丁二酸根等離子僅生成苯甲酸及苯甲酸▊. 己二酸根及壬二酸根離子四種產物皆有.鄰-苯二甲酸根離子主產物為單取代酸▊. 反- 丁烯二酸根, 間-及對-苯二甲酸根離子主產物為雙取代酸▊. 7.有機相氧化▊啶分佈受苯甲醯氯, ▊酸根離子,溫度及有機溶劑影響. 一般言之, 有機相氧化▊啶分佈愈高,反應愈快. 苯甲醯氯效應顯示, 苯甲醯氯濃度愈高,反應速率常數愈小. 8.氧化▊啶催化下,苯甲醯氯-正丁酸鈉與丁酸醯氯-苯甲酸根為兩相間可逆交換反應. 9.無觸媒催化下, 氨基酸根離子與苯甲醯氯可進行快速反應產生醯胺(PhCON(R')RCOOH), 產率高達95%. 氨基酸相對反應活性為 N-甲基氨基乙酸,2-▊咯啶甲酸 >>氨基乙酸, 2-氨基丙酸 > 2-氨基異丁酸 >> 乙酸. 氧化▊啶或對-甲基氨基▊啶催化下, 該反應更快. 10.催化效能 : 反相間轉移觸媒 > 正相間轉移觸媒, 兩者混合使用時顯示相加效果.In this dissertation, the reaction of benzoyl chloride (PhCOCl)and carboxylates in a two-phase water/dichloromethane mediumwas studied using pyridine 1-oxide (PNO) as an inverse phasetrans- fer catalyst. The main goal of this study is toinvestigate the effects of (I) carboxylate ions, (II)dicarboxylate ions, (III) solvent, (IV) dis- tribution of PNO,(V) amino carboxylate ions and (VI) mixed catalyst. The mainconclusions are su- mmarized as follows: 1.Beyond 1100rpm, thereaction rate is independ- ent of the agitation rate . 2.Underappropriate conditions, the reaction of PhCOCl and PNO indichloromethane producing the intermediate is a rate-determining step. 3.The uncatalyzed two-phase reaction ofPhCOCl and carboxylates (or dicarboxylates) is slow and withbenzoic acid as the main product. 4.In the PNO-catalyzedreaction of PhCOCl and RCOONa, the yield of acid anhydride(PhCOOCOR) was generally about 80-90 % . 5.In the PNO-catalyzedreaction of PhCOCl with di- carboxylates, the composition ofproducts depends strongly on the property of dicarboxylate.6.The distribution of free PNO in the organic ph- ase isaffected by PhCOCl, carboxylates, solvent and temperature.7.Two-phase equilibrium reaction is observed in the PNO-catalyzed reaction of PhCOCl and butano- ate ion or of butanoylchloride and benzoate ion. 8.The uncatalyzed reaction ofPhCOCl and amino acid is very fast and produces amide withyield higher than 95 %. The presence of PNO or 4-dime-thylaminopyridine enhances the rate of reaction significantly .9.The order of efficiency of catalysis is inverse phasetransfer (IPT) catalyst >> normal phase transfer (NPT)catalyst. The mixed NPT and IPT catalysts exhibit additiveeffect .