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研究生:陳文欣
研究生(外文):Wen-Shin Chen
論文名稱:反式-[3.3]二硫六氫環及其銅與銀金屬錯化合物的製備與結構探討
論文名稱(外文):Preparation and Structural Analyses of Substituted Dithiahexahydro[3.3] yclophane and It’s Copper(I) and Silver(I) Complexes
指導教授:林孝道
指導教授(外文):Shaw-Tao Lin
學位類別:碩士
校院名稱:靜宜大學
系所名稱:應用化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2005/05/
畢業學年度:93
語文別:中文
論文頁數:127
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cyclophane化合物為具有剛性及兩苯環電子流間互相影響的特性,吸引了不少研究者的興趣。本研究合成苯環-環己烷cyclophane系列化合物及其含取代基與含金屬之衍生物。
利用高稀釋法,分別以α,α’-二溴-2-氯基-對二甲苯與反-1,4-二硫甲基環己烷在乙醇溶液下進行耦合反應而得含取代基之trans-2,11-dithia-4,5,6,7,8,9 -hexahydro-14-chloro[3.3]paracyclophane,藉以1H NMR之光譜性質加以探討具有取代基之cyclophane化合物的剛性及兩環作用力。
然而,本實驗再利用反式-四硫[3.3.3.3]十二氫環化合物作為起始物分別與Cu+、Ag+的IB族金屬化合物,利用不同溶劑緩慢擴散的方式,在兩種溶劑界面形成環金屬錯化合物,並藉由X-Ray單晶繞射探討這些環金屬錯合物的結構。
在透過X-Ray單晶繞射後發現,反式-四硫[3.3.3.3]十二氫環化合物與Cu+、Ag+ 反應生成錯合物之後,形成了各種不同的線狀與網狀結構,我們將以這些不同的結構以X-Ray單晶繞射儀所測出的結果,並與文獻上類似的結構作比較。
Cyclophanes possess the nature of rigidity and the character of electric current the benzene rings, which are able to influence each other between two ring. A number of researchers are interesting in the nature. In this work, a series of substituted trans-dithiahexahydro[3.3]paracyclo- phanes were prepared for structural study.
Under a high-dilute condition, a series of substituted
trans-dithiahexahydro[3.3]paracyclophane were prepared via a coupling reaction of the corresponding trans-1,4-bis(merca-ptomethyl)cyclohexane and substituted 1,4-bis(bromo-methyl)benzene in a 10% ethanolic NaOH solution. Substituted dithiahexahydro[3.3]paracyclophanes were characterized by using of various analytic methods.
Trans-tetrathia-dodecahydro[3.3.3.3]paracyclophane is able to form the complexes with Cu+ or Ag+ by means of two solvents with a slow diffusion process. The structures of those complexes were characterized by using x-ray diffractometer and reuealed the different bonding fashion
中文摘要•••••••••••••••‧‧‧‧‧‧‧••1
英文摘要•••••••••••••••‧‧‧‧‧‧‧••2
緒論•••••••••••••••‧‧‧‧‧‧‧••••3
1.1 研究動機•••••••••‧‧‧‧‧‧‧••••••3
1.2 環化合物的介紹與命名••‧‧‧‧‧‧‧••••••8
1.3 環化合物的特殊性質••‧‧‧‧‧‧‧••••••10
1.4 製備方法••••••••••‧‧‧‧‧‧‧••••15
1.5 環常見的反應•••••••‧‧‧‧‧‧‧••••20
1.6 環的應用•••••••••‧‧‧‧‧‧‧••••27
結果與討論••••••••••••‧‧‧‧‧‧‧••••31
2.1 前言••••••••••••‧‧‧‧‧‧‧••••31
2.2 製備含氯基(-Cl)、溴基(-Br)、碘基(-I)與不含取代基之
二硫環•••••••••‧‧‧‧‧‧‧•••••31
2.3 製備含硝基(-NO2)之二硫環‧‧‧‧‧‧‧•••••35
2.4 光譜性質探討•••••••‧‧‧‧‧‧‧•••••36
2.5 銅與銀的環金屬錯化合物的製備與結構探討•••••48
結論•••••••••‧‧‧‧‧‧‧•••••‧‧••••67
實驗步驟•••••••‧‧‧‧‧‧‧•••••‧‧•••69
3.1 1,4-二羥甲基環己烷-對-甲基苯磺酸鹽(ditosylate)的製備:
化合物46••••‧‧‧‧‧‧‧•••••‧‧••••69
3.2 1,4-二巰甲基環己烷: 化合物48‧‧•••••‧‧•••69
3.3 trans-2,11-Dithia-4,5,6,7,8,9-hexahydro[3.3]paracyclophane
化合物 49 與 trans-2,11,20,29-Tetrathia-4,5,6,7,8,9,22,23,24,25, 26,27-dodecahydro[3.3.3.3]cyclophane 化合物 50
的製備•‧‧‧‧‧‧••••‧‧‧‧••••••‧•70
3.4 1,4-Bis(bromomethyl)-2-chlorobenzene 化合物 54
的製備••••‧‧‧‧‧‧‧•••••‧‧••••72
3.5 1,4-Bis(bromomethyl)-2-bromobenzene 化合物 55
的製備••••‧‧‧‧‧‧‧•••••‧‧••••72
3.6 1,4-Bis(bromomethyl)-2-iodobenzene 化合物 56
的製備••••‧‧‧‧‧‧‧•••••‧‧••••73
3.7 trans-2,11-Dithia-4,5,6,7,8,9-hexahydro-14-chloro [3.3]paracyclophane 化合物 57 與 trans-2,11,20,29-Tetrathia-4,5,6,7,8,9,22,23,24,25,26,27- dodecahydro-14,32-dichloro[3.3.3.3]cyclophane 化合物 60
的製備••••‧‧‧‧‧‧‧•••••‧‧•••••73
3.8 trans-2,11-Dithia-4,5,6,7,8,9-hexahydro-14-bromo [3.3]paracyclophane 化合物 58 與 trans-2,11,20,29-Tetrathia-4,5,6,7,8,9,22,23,24,25,26,27-
dodecahydro-14,32-dibromo[3.3.3.3]cyclophane 化合物 61
的製備••••‧‧‧‧‧‧‧•••••‧‧•••••76
3.9 trans-2,11-Dithia-4,5,6,7,8,9-hexahydro-14-iodo- [3.3]paracyclophane 化合物 59 與 trans-2,11,20,29-Tetrathia-4,5,6,7,8,9,22,23,24,25,26,27- dodecahydro-14,32-diodo[3.3.3.3]cyclophane 化合物 62
的製備••••‧‧‧‧‧‧‧•••••‧‧•••••78
3.10 1,4-Bis(chloromethyl)-2-nitrobenzene 化合物 64
的製備••••‧‧‧‧‧‧‧•••••‧‧••••81
3.11 trans-2,11-Dithia-4,5,6,7,8,9-hexahydro-14-nitro
[3.3]paracyclophane 化合物 65 的製備••••‧‧‧‧82
3.12 Trifluoroacetic silver的製備‧‧‧‧‧•••••‧‧‧‧83
3.13 Di-(μ-iodo)-di(trans-2,11,20,29-tetrathia-4,5,6,7,8,9,22, 23,24, 25,26,27-dodecahydro[3.3.3.3]cyclophane)di-copper(I)
化合物70 的製備•••‧‧‧‧‧‧‧•••••‧‧84
3.14 Trifluoroaceto-(trans-2,11,20,29-tetrathia-4,5,6,7,8,9,22,23,24, 25,26,27-dodecahydro[3.3.3.3]cyclophane)-silver
化合物71 的製備•••‧‧‧‧‧‧‧•••••‧‧84
儀器與藥品•••‧‧‧‧‧‧‧•••••‧‧•••‧‧‧86
4.1 儀器•••‧‧‧‧‧‧‧•••••‧‧•••‧‧‧‧86
4.2 藥品•••‧‧‧‧‧‧‧•••••‧‧•••‧‧‧‧86
參考文獻•••‧‧‧‧‧‧‧•••••‧‧•••‧‧‧‧90
附圖
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