二氯甲烷是實驗室常用的溶劑之一，其性質安定不易發生反應，然
而在零星的文獻及本實驗室的學長的研究發現二氯甲烷發生反應的
例子。
在本篇論文中我們以實驗室宋勇毅學長得到的鋅硫醇錯合物雙三
硫酚磷基鋅化物之四乙基胺鹽 (Et4N)2(PS3Zn)2 及其上的硫醇基與二
氯甲烷反應後得到的亞甲基嵌入雙硫間之產物[(SCH2S)PS]2Zn 為研究
基點。我們首先提出一簡化的單牙基硫醇模型研究硫醇基與二氯甲烷
反應，並詴著在不同鹼性的情況下反應，最後在強鹼的環境下成功的
得到了二氯甲烷反應後的雙硫醚產物，在此反應結果中，能明顯的發
現具有芳香環結構的硫醇是較容易得到雙硫醚產物。之後再加入鋅反
應速率被大幅的抑制，並且於單牙基硫醇的系統中多得到雙硫鍵產
物，因此我們知道鋅在硫醇與二氯甲烷的反應中扮演的是一個抑制劑
的角色。最後我們以加入雙三硫酚磷基鋅化物之四乙基胺鹽
[H3SiPS3]作為學長研究的平行對照，並驗證其與二氯甲烷反應之結果
與大致單牙基硫醇系統之結論大致相同，除了多牙基系統中加入鋅金
屬後仍會形成雙硫醚結構。

Dichloromethane is one solvent that is used widely in laboratory. It is
so stable that it seldom reacts with other materials. There are only a few
reports that involves dichloromehane as a reactant. Previous in our
laboratory, we discovered a dichloromethane activation product.
To study the details of the methylene insertion prouct, [(SCH2S)PS]2Zn
form (Et4N)2 (PS3Zn)2, we used monodentate thiols in different condition
as models to understand what condition thiols may react with dichloro
methane. We found out thiols can react with dichloromethane under
strong base. When there is aromatic ring in a thiol, that thiol will react
with dichloromethane easily. Adding zinc salts showed that zinc ion is
an inhibitor in thiolate/dichloromethane reactions.
We synthesized Tris(3-trimethylsilyl-2-thiophenyl)phosphine [H3SiPS3]
and SiPS3Zn complex to study the parallel effect of adding bulky silyl
substitaents on PS3 ligand towards reaction with dichloromethane. Most
conclusion are similar to that of monodentate thiols. There is one thing
that differs from the results of monedentate thiols: the SiPS3Zn complex
does react with dichloromethane.

中文提要. ii
Abstract...iii
目錄...iv
表目錄...vii
圖目錄...vii
附錄目錄...ix
1. 緒論...1
1-1 前言...1
1-2 單碳化學...1
1-3 鹵烷類化合物在異種偶合反應上之介紹 ...2
1-4 親核性及鹼性...4
1-5 碳硫鍵偶合反應...5
1-6 二氯甲烷反應的例子...10
1-7 研究動機...13
2. 實驗部分...15
2-1 試藥...15
2-2 儀器設備...18
2-3 反應部分...20
2-3-1 配位基 Tris(3-trimethylsilyl-2-thiophenyl)phosphine [H3SiPS3]的合成與鑑定...20
2-3-2 硫醇與二氯甲烷在無鹼的環境...20
2-3-3 硫醇與二氯甲烷在吡啶的環境...21
2-3-3-1 雙硫鍵C6H5S-SC6H5 (1)及雙硫鍵C6H5CH2S-SCH2C6H5 (2)的生成與鑑定...21
2-3-4 硫醇與二氯甲烷在三乙基胺的環境...21
2-3-4-1雙硫醚(C6H5S)2CH2 (3)的生成與鑑定...21
2-3-4-2雙硫醚(o-NH2C6H4S)2CH2 (4)的生成與鑑定...22
2-3-4-3雙硫醚(o-OCH3C6H4S)2CH2 (5)的生成與鑑定...23
2-3-4-4雙硫醚(o-ClC6H4S)2CH2 (6)的生成與鑑定...23
2-3-4-5雙硫醚(C6H4CH2S)2CH2 (7)的生成與鑑定...24
2-3-4-6雙硫鍵C6H11S-SC6H11 (8)的生成與鑑定...25
2-3-4-7雙硫鍵C4H9S-SC4H9 (9)的生成與鑑定...26
2-3-5 硫醇與二氯甲烷在氫化鈉的環境...26
2-3-6 硫醇鈉鹽以1H NMR追蹤之方法...27
2-3-7 H3SiPS3與二氯甲烷在正丁基鋰的環境-產物10之生成與鑑定...27
2-3-8 鋅硫醇鈉鹽與二氯甲烷之追蹤反應-產物2、11及12鑑定...27
2-3-9 化合物(Et4N)2[SiPS3Zn]2 (13) 之生成與鑑定...28
2-3-10 錯合物13與二氯甲烷反應-產物14之生成與鑑定...29
3. 結果與討論...30
3-1 含硫醇化合物與二氯甲烷反應之探討...32
3-1-1硫醇與二氯甲烷於中性環境下反應...32
3-1-2硫醇與二氯甲烷於吡啶之鹼性環境下反應...34
3-1-3硫醇與二氯甲烷於三乙基胺之鹼性環境下反應...34
3-1-4硫醇與二氯甲烷於氫化鈉之鹼性環境下反應...37
3-1-5多牙基磷硫化合物H3SiPS3與二氯甲烷於鹼性環境下之反應...44
3-2 鋅硫醇錯合物與二氯甲烷之反應...46
3-2-1單牙基硫醇鋅錯合物與二氯甲烷之反應...46
3-2-2多牙基硫醇鋅錯合物與二氯甲烷之反應...47
3-2-3二氯甲烷與含硫醇根化合物反應控因探討...50
3-3 單晶結構討論...53
3-3-1 SiPS3Zn(13)與PS3Zn(C)雙聚體比較-矽烷取代基之角色探討...53
3-3-2 雙硫醚及雙硫鍵化合物結晶結構比較...59
4. 結論...67
5. 參考文獻...69

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