期刊論文
| 學年 | 88 |
|---|---|
| 學期 | 2 |
| 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 | en |
| ISSN | 0008-4042 1480-3291 |
| 期刊性質 | |
| 收錄於 | SCI |
| 產學合作 | |
| 通訊作者 | |
| 審稿制度 | |
| 國別 | CAN |
| 公開徵稿 | |
| 出版型式 | 紙本 |
| 相關連結 |
機構典藏連結 ( http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/25388 ) |