臺灣博碩士論文加值系統

摘要
由苯甲醛與三苯化膦及氯二氟乙酸鈉，在高溫下進行Wittig 反應可得β,β-二氟苯乙烯。利用二氟苯乙烯和二溴甲烯進行環化反應形成一新化合物系列的1-芳香基-2-溴-3,3-二氟環丙烯，其二氟環丙烯上Cβ、Cγ的13C NMR化學位移受苯環上取代基(SCS)影響，其SCS可對Hammett常數值(σ)作圖所得：Cγ的斜率為-1.15，相關係數為0.891，表示Cγ受苯環取代基之影響呈現場效應的影響；Cβ的斜率為+6.97，相關係數為0.905，表示Cβ受到苯環取代基共振效應的影響；則Cα沒有線性關係。這顯示環丙烯所含三個碳受到苯環以不同的方式影響。
利用β,β-二氟苯乙烯和溴進行加成反應，得α,β-二溴-β, β-二氟乙烷一系列化合物。由其二氟乙烷系列上的Cα、Cβ的13C NMR化學位移受苯環上取代基影響之分析，依其SCS和Hammett常數(σ)值作圖：Cα的斜率為-2.22，相關係數為0.871，Cβ的斜率為-1.46，相關係數為0.984，表示Cα、Cβ均受苯環取代基之影響呈現場效應的影響。

Abstract
The difluorostyrenes can be prepared in good yield by heating a diglyme solution containing cooresponding aldehyde, triphenylphosphine, and sodium chlorodifluoroacetate. A series of novel 1-aryl-2-bromo- 3,3-difluorocyclopropenes were prepared from the reaction of various difluorostyrenes and bromoform in the presence of an organic base for the study on the substituent-induced chemical shifts (SCS) of C(α,β,γ) using the 13C NMR spectral analyses. The correlation between SCS and Hammett constants (σ) shows that the substituent effect via resonance effect for Cβ ( slope= +6.97, r2= 0.905), and field effect for Cγ ( slope= -1.15, r2= 0.891). No correlation can be made for Cα. 1-Aryl- 2-bromo-3,3-difluorocyclopropenes is readily to react with methanol to form methyl 3-arylpropynoate which is difference from that of trichlorocyclopropene which yields 2-alkoxy-3-arylcyclopropenones.
The aryldibromodifluoroethane were also synthesized from the reaction of various difluorostyrenes and bromine for 13C NMR study. The correlation between SCS and Hammett constants shows that the substituent effect on Cα ( slope= -2.22, r2 = 0.871 ) and Cβ ( slope= -1.46, r2= 0.984 ) via field effect.

文目錄
中文摘要．．．．．．．．．．．．．．．．．．．．．．．I
英文摘要．．．．．．．．．．．．．．．．．．．．．．．．II
第一章 緒論．．．．．．．．．．．．．．．．．．．．．1
1.1 前言．．．．．．．．．．．．．．．．．．．．．1
1.2 環化反應．．．．．．．．．．．．．．．．．． 3
1.3 亞甲基．．．．．．．．．．．．．．．．．．4
1.4 環丙烷(Cyclopropane) ．．．．．．．．．．．．．．7
1.5 環丙烯(Cyclopropene)．．．．．．．．．．．．．．10
1.6 苯基環丙烯．．．．．．．．．．．．．．．．．．11
1.7 鹵基環丙烷的化學反應．．．．．．．．．．．．．13
1.8 鹵基環丙烯的化學反應．．．．．．．．．．．．14
1.9 Wittig反應．．．．．．．．．．．．．．．．．16
1.10 質譜法(Mass Spectrometry,MS)．．．．．．．．．．18
1.11 核磁共振光譜術(NMR)．．．．．．．．．．．．．20
1.12 Hammett方程式．．．．．．．．．．．．．．．．21
第二章 結果與討論．．．．．．．．．．．．．．．．．．23
2.1 氯二氟乙酸鈉的製備．．．．．．．．．．．．．．．23
2.2 β,β-二氟苯乙烯的製備．．．．．．．．．．．．．24
2.3 1-芳香基-2-溴-3,3-二氟環丙烯的製備．．．．．．．．30
2.4 1-芳香基-2-溴-3,3-二氟環丙烯的化學反應．．．．．．40
2.5 β,β-二氟苯乙烯加溴反應．．．．．．．．．．．．42
第三章 結論．．．．．．．．．．．．．．．．．．．．．51
第四章 實驗步驟與數據．．．．．．．．．．．．．．．．53
4.1 氯二氟乙酸鈉鹽的製備．．．．．．．．．．．．．53
4.2-1 β,β-二氟苯乙烯之製備．．．．．．．．．．．．53
4.2-2 β,β-二氟苯乙烯的光譜數據．．．．．．．．．．55
4.3-1 1-芳香基-2-溴-3,3-二氟環丙烯製備．．．．．．．．61
4.3-2 1-芳香基-2-溴-3,3-二氟環丙烯的光譜數據．．．．．63
4.4-1 1-芳香基-2-溴-3,3-二氟環丙烯的甲醇化反應．．．．71
4.4-2 3-芳香基丙炔酸甲酯的光譜數據．．．．．．．．．72
4.5-1 β,β-二氟苯乙烯與溴反應．．．．．．．．．．．74
4.5-2 α-芳香基-α,β-二溴-β,β-二氟乙烷的光譜數據．．75
4.5-3 2-溴-5-甲氧基-β,β-二鹵苯乙烯．．．．．．．．．81
第五章 儀器與藥品．．．．．．．．．．．．．．．．．．83
5.1 儀器．．．．．．．．．．．．．．．．．．．．．83
5.2 藥品．．．．．．．．．．．．．．．．．．．．．84
第六章 參考文獻．．．．．．．．．．．．．．．．．．．89
第七章 附圖．．．．．．．．．．．．．．．．．．．．．95

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