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dc.contributor.author陳良吉en_US
dc.contributor.authorLiang-Jyi Chenen_US
dc.contributor.author鍾文聖en_US
dc.contributor.authorWen-Sheng Chungen_US
dc.date.accessioned2014-12-12T02:14:08Z-
dc.date.available2014-12-12T02:14:08Z-
dc.date.issued1994en_US
dc.identifier.urihttp://140.113.39.130/cdrfb3/record/nctu/#NT830500028en_US
dc.identifier.urihttp://hdl.handle.net/11536/59605-
dc.description.abstract本研究的長期目標是合成一個穩定的 non-Kekule 雙自由基分子的前驅
物,來探討雙自由基分子 (13) 的基態.在成功合成目標物 1,4-雙氫口夫
喃并[3,4-d]2,3-口咢口塞-2-氧化合物(34)(1,4-Dihydro- furano[3,4-
d]2,3-oxathiin-2-oxide)後,我們同時也對此化合物進行熱化學的研究,
來探討此化合物與其異構物 4,6-雙氫口塞吩[3,4-c]口夫喃-5,5-雙氧(4
H,6H-Thieno[3,4-c]Furan-5,5-dioxide) 反應性的異同.此外,我們也合
成 1,4-雙氫-5,6-苯并-2,3-口咢口塞-2-氧化合物 (1,4-Dihydro-5,6-
benzo-2,3-oxathiin-2-oxide)來建立sultine系列的研究範疇.由實驗的
結果,我們發現 1,4-雙氫口夫喃并[3,4-d] 2,3-口咢口塞-2-氫化合物
在 140℃的反應溫度範圍內,似乎遵循著 4,6 -雙氫口塞吩[3,4-c] 口夫
喃-5,5-雙氧的反應機構,也就是先進行 Diels-Alder 加成反應,然後脫
去 SO2,形成橋式 (Type A)產物。但在 N-phenylmaleimide 為親雙烯基
時,它繼續進行第二次 Diels-Alder 加成,而僅生成 Type B 產物為主
。但在更高溫度下,仍可能進行雙自由基分子的機構。然而,進一步的結
果,仍需借助於雷射瞬間光解法加以證實。而 1,4-雙氫-5,6 -苯并-2,3-
口咢口塞-2-氧化合物在150℃的反應溫度範圍內,就如文獻所述一般是先
生成二甲烯苯(o-quinodimethane)後,再進行 Diels-Alder 反應,形成
加成產物。
The long term goal of this work is to find a stable precursor
for non-Kekule biradical (13) to study it's ground state mult-
tiplicity. After sucessfully making our target molecule furan-
sultine (1,4-Dihydrofurano[3,4-d]2,3-2-oxide; 34), we studied
the thermolysis of (34) and it's isomer, furan-sulfolene (35)
, in the presence and absence of alkenes and alkynes. We also
studied the chemisty of benzosultine (33) for comparison. Below
140℃,uransultine (34) and furansulfolene (35) seem to follow
same reaction mechanisms, i.e. firstly, they undergo Diels-
Alder reactions with alkenes (or alkynes) on the furan ring and
then undergo SO2 extrusion to form mostly Type A (bridged)
products. In the case of N-phenylmaleimide the bridged product
undergoes a second Diels-Alder reaction to form Type B compound
as the only isolated product. At higher Temperature (T>140℃),
however, the involvement of diradical intermediate is possible.
Which needs to he proved by laser flash photolysis method. In
the temperature range strdied (T≧140℃), benzosultine (33)
undergoes Diels-Alder reaction via the ortho-quinodimethane
intermediate (1) as described in the literatrue.
zh_TW
dc.language.isozh_TWen_US
dc.subject雙自由基分子,二甲烯苯zh_TW
dc.subjectnon-Kekule,biradial,Diels-Alder,o-qunodimethaneen_US
dc.title1,4-雙氫口夫喃并[3,4-d]2,3-口咢口塞-2-氧化合物的合成及它在 Diels-Alder 反應上的應用zh_TW
dc.titleThe Synthesis of 1,4-Dihydrofurano[3,4-d]2,3-oxathiin-2-oxide and it's Application in Diels-Alder Reactionen_US
dc.typeThesisen_US
dc.contributor.department應用化學系碩博士班zh_TW
Appears in Collections:Thesis