環對苯雙烯之合成及性質鑑定｜國立臺灣科技大學博碩士論文系統

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研究生：	余陞豪 Sheng-hao Yu
論文名稱：	環對苯雙烯之合成及性質鑑定 Synthesis and Characterization of Cyclophanedines
指導教授：	游進陽 Chin-yang Yu
口試委員:	邱顯堂 Hsien-tang Chiu 游進陽 Chin-yang Yu 堀江正樹 Masaki Horie
學位類別：	碩士 Master
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2013
畢業學年度：	101
語文別：	英文
論文頁數：	212
中文關鍵詞：	環對苯雙烯、環雙烯、環張力
外文關鍵詞：	cyclophanediene, dithiacyclophane
相關次數：	點閱：112 下載：0
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本論文目的主要合成含有辛烷氧基之四取代環對苯雙烯、環對萘雙烯和不對稱結構之環對萘苯雙烯分子，並對這些具有環張力性質之單體進行基本結構鑑定。以上三個單體可利用其前驅物：dithiacyclophanes、dithianaphthalenephanes 與 dithianaphthalene cyclophanes經由分子內重排及氧化反應，最後進行熱分解而製得環雙烯單體，其非鏡像立體異構物(pseudo germinal與pseudo ortho form)可經由管柱層析法或再結晶進行分離。最後藉由核磁共振儀(NMR)、質譜(Mass)和愛克斯射線單晶繞射儀(single crystal)證明這些單體結構，且這些非鏡像立體異構物的單晶結構一致顯示了芳香環是強烈被扭曲的且具有高水準的環張力。

The aim of this thesis was to synthesize and characterization of tetraoctyloxy substituted [2.2]paracyclophane-1,9-dienes, tetraoctyloxy substituted [2.2]paranaphthalenephane-1,9-dienes and tetraoctyloxy substituted [2.2]naphthalene paracyclophane-1,9-dienes based monomers. The three monomers can be prepared in three steps from dithia[3.3]paracyclophanes, dithia[3.3]paranaphthalenephane or dithia[3.3]naphthalene paracyclophanes. A mixture of pseudo-geminal and pseudo-ortho diastereomers is produced and the pure compounds by column chromatography and recrystallization. We can determine their structure is right from NMR, Mass and X-ray crystal structure. The solid state structures of these diastereomers reveal strongly distorted aromatic rings consistent with high levels of ring strain.

Chapter 1. Introduction and Aims	1
1 Introduction	2
2 Introduction to paracyclophanes	2
2.1 Cyclophanes	2
1.2 [2.2]paracyclophane-1,9-diene	4
1.3 X-ray crystal structure of [2.2]paracyclophanes	5
3 Ring opening metathesis polymerization	7
3.1 Monomers for ROMP	9
3.2 Catalysts for ROMP	9
3.2 Polymers through ROMP	11
4 Aims of the project	14
5 References	15
Chapter 2. Synthesis and Characterisation of Cyclophanediene-Based Monomers	18
1 Synthesis and characterization	19
1.1 Tetraoctyloxy substituted paracyclophanediene	19
1.2 Tetraoctyloxy substituted paranaphthalenephandiene	27
1.3 Tetraoctyloxy substituted [2.2]naphthalene paracyclophane diene	35
2 References	48
Chapter 3. Conclusions and Future Investigations	49
1 Conclusions	50
2 Future Investigations	50
Chapter 4. Experimental	52
1 General procedures	53
2 Synthesis	53
2.1 Synthesis of tetraoctyloxy substituted paracyclophanediene	54
2.1.1 Synthesis of 1,4-dioctyloxybenzene (1.1)	54
2.1.2 Synthesis of 2,5-bis(bromomethyl)-1,4-dioctyloxybenzene (1.2)	54
2.1.3 Synthesis of 2,5-bis(thiolatomethyl)-1,4-dioctyloxybenzene (1.3)	55
2.1.4 Synthesis of 5,8,14,17-tetraoctyloxy-2,11-dithia[3.3]paracyclophane (1.4a) and 6,9,14,17-tetraoctyloxy-2,11-dithia [3.3]paracyclophane (1.4b)	56
2.1.5 Synthesis of compound (1.5)	57
2.1.6 Synthesis of compound (1.6)	57
2.1.7 Synthesis of 4,7,12,15-tetraoctyloxy-[2.2]paracyclophane-1,9 -diene (1.7a) and 5,8,12,15-tetraoctyloxy-[2.2]paracyclophane-1,9 -diene (1.7b)	58
2.2 Synthesis of tetraoctyloxy substituted paranaphthalene phan- diene	59
2.2.1 Synthesis of 2,6-Dibromo-1,5-dithydroxynaphthalene (2.1)	59
2.2.2 Synthesis of 2,6-bis(bromomethyl)-1,5-bis(octyloxy)naphthalene (2.2)	60
2.2.3 Synthesis of 1,5-bis(octyloxy)naphthalene-2,6-dicarbaldehyde (2.3)	60
2.2.4 Synthesis of 1,5-bis(octyloxy)naphthalene-2,6-dihydroxymethyl (2.4)	61
2.2.5 Synthesis of 2,6-bis(bromomethyl)-1,5-bis(octyloxy)naphthalene (2.5)	62
2.2.6 Synthesis of 2,6-bis(thiolatomethyl)-1,5-bis(octyloxy)naphthalene (2.6)	62
2.2.7 Synthesis    of     5,9,16,20-tetraoctyloxy-2,11-dithia[3.3] paranaphthalenephane (2.7)	63
2.2.8 Synthesis of compound (2.8)	64
2.2.9 Synthesis of compound (2.9)	65
2.2.10 Synthesis of 4,8,14,18-tetraoctyloxy-[2.2]paranaphthalenephane-1,11- diene (2.10a) and 4,8,16,20-tetraoctyloxy-[2.2]paranaphthalenephane- 1,11-diene (2.10b)	65
2.3 Tetraoctyloxy substituted [2.2]naphthalene paracyclophane- diene	67
2.3.1 Synthesis  of  5,9,16,19-tetraoctyloxy-2,13-dithia[3.3]naphthalene paracyclophane (3.1a) and 5,9,17,20-tetraoctyloxy-2,13-dithia [3.3]naphthalene paracyclophane (3.1b)	67
2.3.2 Synthesis of compound (3.2)	68
2.3.3 Synthesis of compound (3.3)	69
2.3.4 Synthesis     of      4,8,14,17-tetraoctyloxy-[2.2]naphthalene paracyclophane-1,11-diene (3.4a) and 4,8,15,18-tetraoctyloxy- [2.2]naphthalene paracyclophane- 1,11-diene (3.4b).	70
Appendix.	72
1H, 13C NMR and Mass spectrum	72
Single crystals X-ray crystallography	99

                                

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