教師資料查詢 | 類別: 期刊論文 | 教師: 林雲山 LIN, YUN-SHAN (瀏覽個人網頁)

標題:Theoretical studies of azulene and its derivatives
學年
學期
出版(發表)日期2000/02/01
作品名稱Theoretical studies of azulene and its derivatives
作品名稱(其他語言)
著者Wang, Bo-cheng; Lin, Yun-shan; Chang, Jian-chuang; Wang, Pei-yu
單位淡江大學化學學系
出版者Ottawa, ON: NRC Research Press
著錄名稱、卷期、頁數Canadian journal of chemistry 78(2), pp.224-232
摘要The results of ab initio calculations with the 6-31G basis sets on azulene and its derivatives (including azulenequinones and diazoazulenequinones) are presented in accordance with considerations of their structures and bonding. Azulene is a non-alternant compound with ten π electrons and has either a Cs or C2v symmetry depending on the different carbon bonding. The semiempirical and HF ab initio calculations converge to a Cs symmetry and the DFT and MP2 calculations converge to a C2v symmetry as a ground state structure of azulene. The CIS calculations describe the excited state of azulene and the first excitation energy (S0 - S1) is 533 nm (CIS/6-31+G*), which could illustrate the azure color of azulene. According to the geometry analysis, there are 16 geometrical isomers in azulenequinone conjugated diketones of azulene. Ab initio calculation with the 6-31G basis set generates 1,5- and 1,7-azulenequinone being the most stable isomers of azulenequinone. Theoretically, the relative stability of the bromination product of azulenequinones indicates that 7-bromo-1,5-azulenequinone and 3-bromo-1,7- azulenequinone (for monobromoazulenequinones) and 3,7-dibromo-1,5- azulenequinone and 3,5-dibromo-1,7-azulenequinone (for dibromoazulenequinones) are more stable isomers. The product of diazotization of amino- bromoazulenes is diazoazulenequinone in which a diazo group replaces a ketone group. Isomeric 1,8- and 1,2-diazoazulenequinones are the most stable isomers of diazoazulenequinone according to the theoretical consideration. Due to the resonance and relative stability, diazoazulenequinone may easily extrude nitrogen and form the corresponding triplet ketocarbene intermediate and electronic isomers that undergo photoreaction with THF leading to a polyether bridged azulene (crown type ether). The cyclic reactions in diazoazulenequinone are also studied.Key words: azulene, azulenequinone, diazoazulenequinone, ab initio.
關鍵字
語言英文
ISSN0008-4042;1480-3291
期刊性質
收錄於SCI
產學合作
通訊作者
審稿制度
國別加拿大
公開徵稿
出版型式紙本
相關連結
SDGs
Google+ 推薦功能,讓全世界都能看到您的推薦!