臺灣博碩士論文加值系統

本次研究分三系列，第一系列是以合成出含唑基為主並含側鏈基團，側鏈基團為n個柔軟間距的烷氧基，1,3,5-三[5-(3,4,5-三烷氧苯基)-1,3,4-唑-2-基]苯，TPOB3-n(n=3~12)(Scheme Ⅰ)、1,3,5-三[5-(3,4-二烷氧苯基)-1,3,4-唑-2-基]苯，TPOB2-n(n=3~12)(Scheme Ⅱ)及1,3,5-三[5-(3-烷氧苯基)-1,3,4-唑-2-基]苯，TPOB1-n(n=3~ 12) (Scheme Ⅲ)皆是先合成出含四唑基的中間體，再與苯甲醯氯在吡啶中反應得TPOB3-n(n=3~12)、TPOB2-n(n=3~12)及TPOB1-n(n=3~12)。
第二系列是以雙苯[2,3-a:2′,3′-c]二苯駢為中心核並含八個側鏈基團， 2,3,6,7,2′,3′,6′,7′-八烷氧基[11,11′]雙苯[2,3-a:2′,3′-c]二苯駢，ODBPAZ-n (n=4~12)(Scheme Ⅳ)。先合成其中間產物2,3,6,7-四烷氧基菲-9,10-雙酮，在醋酸溶液中與3,3′-雙胺基聯苯胺得ODBPAZ-n(n=4~12)。
第三系列是以雙苯[b:i]-1,4,6,9,-四偶氮為中心核並含八個側鏈基團，2,3,6,7,13,14,17,18-八烷氧基-雙苯[b:i]- 1,4,6,9,-四偶氮，ODPTAA-n (n=4~12,14)(Scheme Ⅴ)。先合成中間體2,3,7,8-四[3,4-雙-烷氧基苯]- 1,4,6,9-四偶氮，再氧化得ODPTAA-n (n=4~12,14)。
合成的化合物皆經由NMR、質譜儀及紅外線光譜儀鑑定其結構，並利用DSC、POM及X-ray繞射鑑定其液晶相變化及排列情形。化合物TPOB3-n(n=3~12)、TPOB2-n(n=5~12)及ODPTAA-n (n= 4~12,14)為不規則六角柱狀排列(Colh)。而ODBPAZ-n(n=4~12)為四角柱狀排列(Colt)。TPOB1-n (n=3~12)因為側鏈烷氧基數目較少致使分子間有較大的自由空間，而減少了其排列為柱型的能力，但因為分子間的作用力使其能形成盤狀向列型排列(ND)。而具短鏈長的化合物TPOB2-n(n=3,4)也是盤狀向列型排列(ND)。

Three series of discotic liquid crystals with alkyl side chain from 3~12 carbon atoms were prepared and characterized.
In the series Ⅰ, three types of discotic liquid crystals with changing the number of flexible long alkyl chains in the surroundings of a 1,3,5-tris(5-phenyl) -1,3,4-oxadiazol-2-yl)benzene core were synthesized: 1,3,5-tris[5-(3,4,5-trialkoxy phenyl)-1,3,5-oxadiazol-2-yl]benzene,TPOB3-n(n=3~12)(R1=R2=R3=OCnH2n+1) (Scheme Ⅰ). 1,3,5-Tris[5-(3,4-dialkoxyphenyl)-1,3,5-oxadiazol-2-yl]benzene, TPOB2-n(n=3~12)(R1=R2=OCnH2n+1 and R3=H)(Scheme Ⅱ) and 1,3,5-tris[5-(4- alkoxyphenyl)-1,3,5-oxadiazol-2-yl]benzene, TPOB1-n(n=3~12) (R1= R3=H and R2= OCnH2n+1)(Scheme Ⅲ).
In the series Ⅱ, the family of disc like compounds, 2,3,6,7,2′,3′,6′,7′- Octa-butyloxy[11,11′]dibenzo[2,3-a:2′,3′-c]phenazines, ODPTAZ-n(n=4~12)(Scheme Ⅳ),which have been now synthesized by direct conversion of the corresponding 2,3,6,7-tetrakis(alkoxy)phenathrone-9,10-dione with 3,3′-diaminobenzidine.
In the series Ⅲ, new discogens based on the diphenanthro[b:i]-1,4,6,9- tetraazaanthracene, ODPTAA-n(n=4~12,14)(Scheme Ⅴ) were prepared in two-step synthesis by reaction of the bis(3,4-dialkoxy)benzil with 1,2,4,5-tetraaminobenzene and subsequent oxidative aryl-aryl coupling with VOF3 in the presence of boron trifluoride-diethylether.
All these compounds were characacterized by IR, mass, 1H and 13C NMR spectroscopies, and their mesomorphic behaviors were examined with DSC, polarized optical microscopy and X-ray diffraction. Compounds TPOB3-n(n=3~12), TPOB2-n (n=5~12), and ODPTAA-n(n=4~12,14) show hexagonal disordered mesophases (Colh). Whereas, the homogolous compounds ODBPAZ-n(n=4~12) show columnar tetragonal mesophases (Colt). On the other hand, a broad spectrum of homologous 1,3,5-tris[5-(4-alkoxyphenyl)-1,3,5-oxadiazol-2-yl]benzene derivatives, TPOB1-n(n= 3~12) exhibited disk-like nematic mesophase with three peripheral alkoxy moieties. Thus, in the case of the compounds TPOB1-n(n=3~12) there is a lot of free-space around the core that reduces the ability of the molecules to pack in a columnar fashion, but intermolecular interactions are still sufficient to enable the exhibition of the ND phase. However, the compound TPOB2-n(n=3,4) with six peripheral short length of propoxyloxy and butyloxy groups also showed the ND phase.

中文摘要
英文摘要
誌謝
目錄
List of Scheme
List of Figure
List of Table
第一章 緒論
1.1 前言……………………………………………………… 1
1.2 盤狀液晶簡介………………………………………….... 2
1.3 盤狀液晶分類…………………………………………… 3
1.4 液晶化合物的化學構成及其性質……………………… 7
1.5 液晶相之鑑定…………………………………………… 11
1.6 研究動機與目的…………………………………………14
第二章 實驗
2.1 藥品………………………………………………………18
2.2 實驗儀器與測試方法……………………………………18
2.3 合成方法…………………………………………………27
第三章 結果
3.1 單體之合成與鑑定………………………………47
3.2 液晶相之鑑定與其物性之探討……………….97
3.3 X-ray之探討…………………………………………….99
3.4 光學性質之探討………………………………………. 101
第四章 討論……………………………………………………...130
第五章 總結………………………………………………………146
參考資料………………………………………………………………147
List of Scheme
Scheme Ⅰ The synthesis of TPOB3-n…………………………22
Scheme Ⅱ The synthesis of TPOB2-n…………………………23
Scheme Ⅲ The synthesis of TPOB1-n…………………………24
Scheme Ⅳ The synthesis of ODBPAZ-n………………………25
Scheme Ⅴ The synthesis of ODPTAA-n………………………26
List of Figure
Fig.1-1 Subclassification of discotic liquid crystals according molecular aggregation…………………………………..4
Fig.1-2 Schematic representation of different type of
Mesophases……………………………………………...5
Fig.1-3 Schmatic representation of hexagonal mesophases……..6
Fig.1-4 Characterization of discotic liquid crystals……………...9
Fig.1-5 Characterization of discotic liquid crystals…………….10
Fig.1-6 Characterization of discotic liquid crystals…………….17
Fig.3.1-1 Mass specrum of compound 3,4,5-tris-octyloxy-
Benzamide……………………………………………..54
Fig.3.1-2 IR spectrum of compound 3,4,5-tris(octyloxy)
Benzamide……………………………………………..55
Fig.3.1-3 1H-NMR spectrum of compound 3,4,5-tris(octyloxy)
Benzamide……………………………………………..56
Fig.3.1-4 13C-NMR spectrum of compound 3,4,5-tris(octyloxy)
Benzamide……………………………………………..57
Fig.3.1-5 Mass specrum of compound 3,4,5-tris(octyloxy)
Benzonitrile…………………………………………….58
Fig.3.1-6 IR spectrum of compound 3,4,5-tris(octyloxy)
benzonitrile……………………………………………..59
Fig.3.1-7 1H-NMR speutrum of compound 3,4,5-tris(octyloxy) benzonitrile……………………………………………..60
Fig.3.1-8 13C-NMR spectrum of compound 3,4,5-tris(octyloxy) benzonitrile……………………………………………..61
Fig.3.1-9 Mass specrum of compound 5-[3,4,5-tris(octyloxy)phenyl] tetrazole………………………………………………..62
Fig.3.1-10 1H-NMR speutrum of compound 5-[3,4,5-tris(octyloxy)
phenyl] tetrazole……………………………………..63
Fig.3.1-11 13C-NMR spectrum of compound 5-[3,4,5-tris(octyloxy)
phenyl] tetrazole……………………………………..64
Fig.3.1-12 Mass specrum of compound 1,3,5-tris[5-(3,4,5-tri(octyloxy)
phenyl)-1,3,4-oxadiazol-2-yl]benzene………………..65
Fig.3.1-13 IR spectrum of compound 1,3,5-tris[5-(3,4,5-tri(octyloxy)
phenyl)-1,3,4-oxadiazol-2-yl]benzene………………66
Fig.3.1-14 1H-NMR speutrum of compound 1,3,5-tris[5-(3,4,5-tri (octyloxy)phenyl)-1,3,4-oxadiazol-2-yl]benzene……67
Fig.3.1-15 13C-NMR spectrum of compound 1,3,5-tris[5-(3,4,5-tri (octyloxy) phenyl)-1,3,4-oxadiazol-2-yl]benzene……68
Fig.3.1-16 Mass specrum of compound 3,4-bis(octyloxy)
Benzonitrile…………………………………………..69
Fig.3.1-17 IR spectrum of compound 3,4-bis(octyloxy)
benzonitrile…………………………………………...70
Fig.3.1-18 Mass specrum of compound 5-[3,4-bis(octyloxy) phenyl]
Tetrazole………………………………………………71
Fig.3.1-19 Mass specrum of compound 1,3,5-tris[5-(3,4-di(octyloxy) phenyl)-1,3,4-oxadiazol-2-yl]benzene………………..72
Fig.3.1-20 IR spectrum of compound 1,3,5-tris[5-(3,4-di(octyloxy) phenyl)-1,3,4-oxadiazol-2-yl]benzene………………..73
Fig.3.1-21 1H-NMR speutrum of compound 1,3,5-Tris[5-(3,4-di- octyloxy- phenyl)-1,3,4-oxadiazol-2-yl]benzene……..74
Fig.3.1-22 13C-NMR spectrum of compound 1,3,5-Tris[5-(3,4-di- octyloxy- phenyl)-1,3,4-oxadiazol-2-yl]benzene……..75
Fig.3.1-23 IR spectrum of compound 4-octyloxybenzonitrile……...76
Fig.3.1-24 Mass specrum of compound 5-(4-octyloxyphenyl)-
Tetrazole………………………………………………77
Fig.3.1-25 Mass specrum of compound 1,3,5-tris[5-(4-octyloxyphenyl)-
1,3,4-oxadiazol-2-yl]benzene…………………………78
Fig.3.1-26 IR spectrum of compound 1,3,5-tris[5-(4-octyloxyphenyl)-
1,3,4-oxadiazol-2-yl]benzene…………………………79
Fig.3.1-27 1H-NMR speutrum of compound 1,3,5-tris[5-(4-octyloxy phenyl)-1,3,4-oxadiazol-2-yl]benzene……………….80
Fig.3.1-28 13C-NMR spectrum of compound 1,3,5-tris[5-(4-octyloxy- phenyl)-1,3,4-oxadiazol-2-yl]benzene……………….81
Fig.3.1-29 Mass specrum of compound 3,3′,4,4′-tetra(octyloxy)
Benzil…………………………………………………82
Fig.3.1-30 IR spectrum of compound 3,3′,4,4′-Tetra(octyloxy)
Benzil…………………………………………………83
Fig.3.1-31 1H-NMR speutrum of compound 3,3′,4,4′-tetra(octyloxy) benzil………………………………………………….84
Fig.3.1-32 13C-NMR spectrum of compound 3,3′,4,4′-tetra(octyloxy) benzil………………………………………………….85
Fig.3.1-33 Mass specrum of compound 2,3,6,7-tetrakis(octyloxy) phenanthrene-9,10-dione……………………………...86
Fig.3.1-34 IR spectrum of compound 2,3,6,7-tetrakis(octyloxy) phenanthrene-9,10-dione………………………………87
Fig.3.1-35 1H-NMR speutrum of compound 2,3,6,7-tetrakis-octyloxy- phenanthrene-9,10-dione………………………………88
Fig.3.1-36 13C-NMR spectrum of compound 2,3,6,7-tetrakis-octyloxy- phenanthrene-9,10-dione………………………………89
Fig.3.1-37 Mass specrum of compound 2,3,6,7,2′,3′,6′,7′-octa- octyloxy[11,11′]dibenzo[2,3-a:2′,3′-c]phenazine……...90
Fig.3.1-38 1H-NMR speutrum of compound 2,3,6,7,2′,3′,6′,7′-octa- octyloxy[11,11′]dibenzo[2,3-a:2′,3′-c]phenazine………91
Fig.3.1-39 13C-NMR spectrum of compound 2,3,6,7,2′,3′,6′,7′-octa- octyloxy[11,11′]dibenzo[2,3-a:2′,3′-c]phenazine………92
Fig.3.1-40 1H-NMR speutrum of compound 2,3,7,8-tetrakis[3,4-di- octyloxyphenyl]-1,4,6,9-tetraazaanthracene……………93
Fig.3.1-41 13C-NMR spectrum of compound 2,3,7,8-tetrakis[3,4-di- octyloxyphenyl]-1,4,6,9-tetraazaanthracene……………94
Fig.3.1-42 1H-NMR speutrum of compound 2,3,6,7,13,14,17,18-octa- octyloxy-diphenanthro[b:i]-1,4,6,9,-
tetraazaanthracene………………………………………95
Fig.3.1-43 13C-NMR spectrum of compound 2,3,6,7,13,14,17,18-octa- octyloxy-diphenanthro[b:i]-1,4,6,9,-
tetraazaanthracene………………………………………96
Fig.3.2-1 DSC thermograms for TPOB3-6 and TPOB3-8…………104
Fig.3.2-2 Polarized optical micrograph of TPOB3-n, cooled from the isotropic phase………………………………………..105
Fig.3.2-3 DSC thermograms for TPOB2-6 and TPOB2-8………..107
Fig.3.2-4 Polarized optical micrograph of TPOB2-n, cooled from the isotropic phase………………………………………..108
Fig.3.2-5 Polarized optical micrograph of TPOB2-n, cooled from the isotropic phase………………………………………..109
Fig.3.2-6 DSC thermograms for TPOB1-6 and TPOB1-8………..111
Fig.3.2-7 Polarized optical micrograph of TPOB1-n, cooled from the isotropic phase………………………………………..112
Fig.3.2-8 DSC thermograms for ODBPAZ-8 and ODPTAA-8…...114
Fig.3.2-9 Polarized optical micrograph of ODBPAZ-n, cooled from the isotropic phase………………………………………..115
Fig.3.2-10 Polarized optical micrograph of ODBPAZ-n, cooled from the isotropic phase………………………………………..116
Fig.3.2-11 Polarized optical micrograph of ODPTAA-n, cooled from the isotropic phase……………………………………118
Fig.3.3-1 X-ray diffraction pattern of TPOB3-8(n=8)……………119
Fig.3.3-2 X-ray diffraction pattern of TPOB2-8(n=8)……………120
Fig.3.3-3 X-ray diffraction pattern of TPOB1-8(n=8)……………121
Fig.3.3-4 X-ray diffraction pattern of ODBPAZ-8(n=8)………….122
Fig.3.3-5 X-ray diffraction pattern of ODPTAA-12(n=12)……….123
Fig.3.4-1 Absorption and photoluminescent spectra of TPOB3-8..125
Fig.3.4-2 Absorption and photoluminescent spectra of TPOB2-8..126
Fig.3.4-3 Absorption and photoluminescent spectra of TPOB1-8..127
Fig.3.4-4 Absorption and photoluminescent spectra of
ODBPAZ-8……………………………………………...128
Fig.3.4-5 Absorption and photoluminescent spectra of
ODPTAA-8……………………………………………...129
Fig.4-1 Dependence of the transition temperature on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline TPOB3-n(n=3~12)…………………………..134
Fig.4-2 Effect of the entropy change on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline
TPOB3-n(n=3~12)………………………………………135
Fig.4-3 Dependence of the transition temperature on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline TPOB2-n(n=3~12)…………………………136
Fig.4-4 Effect of the entropy change on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline
TPOB2-n(n=3~12)……………………………………..137
Fig.4-5 Dependence of the transition temperature on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline TPOB1-n(n=3~12)………………………….138
Fig.4-6 Effect of the entropy change on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline
TPOB1-n(n=3~12)………………………………………139
Fig.4-7 Dependence of the transition temperature on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline ODBPAZ-n(n=4~12)…………………………140
Fig.4-8 Effect of the entropy change on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline
ODBPAZ-n(n=4~12)……………………………………..141
Fig.4-9 Dependence of the transiton temperatures on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline ODBPAZ-n(n=5~12) and TPBQ-n(n=5~12)…142
Fig.4-10 Dependence of the transition temperature on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline ODPTAA-n(n=4~12,14)……………………...143
Fig.4-11 Effect of the entropy change on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline
ODPTAA-n(n=4~12,14)………………………………….144
Fig.4-12 Dependence of the transiton temperatures on n, the number of carbons on alkoxy group for the series of discotic liquid crystalline ODBPAZ-n(n=4~12) and TPBQ-n(n=4~12)….145
List of Table
Table 3.2-1 Thermal transitions and thermodynamic parameters of TPOB3-n……………………………………………...103
Table 3.2-2 Thermal transitions and thermodynamic parameters of
TPOB2-n………………………………………………106
Table 3.2-3 Thermal transitions and thermodynamic parameters of
TPOB1-n………………………………………………110
Table 3.2-4 Thermal transitions and thermodynamic parameters of
ODBPAZ-n……………………………………………113
Table 3.2-5 Thermal transitions and thermodynamic parameters of
ODPTAA-n……………………………………………117
Table 3.4-1 Photoluminescent and absorption……………………...124

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