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The reaction mechanism, thermodynamic and kinetic behavior of the dipole cycloaddition reaction of benzaldoxime with propinol have been studied by DFT method at B3LYP/6-31G* level.
用密度泛函理论方法在B3LYP/6-31G*水平上研究了苯甲醛肟与炔丙醇加成反应的微观机制和热力学、动力学行为。
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The results show that there are eight reaction channels, corresponding to eight transition states, in the reaction process. The main parts of all transition states are non-planar five-membered ring, in which the geometry of Z -benzaldoxime and E -benzaldoxime is maintained partially, but the bond length, bond angle and charge are all changed.
结果表明,在苯甲醛肟与炔丙醇加成反应过程中, 8个可能反应通道的过渡态中均形成非平面五元环结构,其中苯甲醛肟的 Z 、 E 构型特征得到了部分保留,但主要部分的键长、键角均发生了变化,电荷也进行了重新分布。
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The four reaction channels including hydroxyl-type benzaldoxime are endothermic reaction, thermodynamically non-spontaneous process, but the other four reaction channels including ion-type benzaldoxime participation are exothermic reaction and thermodynamically spontaneous process. The latter four reaction channels, which have lower reaction barriers, faster reaction velocities and bigger equilibrium constants than those of the former fours, are the chief reaction channels.
苯甲醛肟以羟基型参与反应的4个反应通道均为吸热反应和热力学非自发过程,它们均具有较高的反应势垒、较慢的反应速率和较小的平衡常数;而以离子型参与反应的四个反应通道均为放热反应和热力学自发过程,它们的反应势垒较低,反应速度较快,平衡常数也较大,故苯甲醛肟应主要以离子型参与反应。
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The intermediate which obtained from oximation of 7a-e reacted withmethyl N-(2-bromomethylphenyl)-N-methoxycarbamate to synthesize oxime ether methyl carbamate 3a-e.
以邻位卤代苯甲醛和3-丁烯-2-醇为原料通过钯催化&一锅法&反应合成了2-乙酰基茚7a-e,7a-e 肟化之后和N-(2-溴甲基苯基)-N-甲氧基氨基甲酸甲酯反应合成了肟醚类氨基甲酸甲酯3a-e,进一步胺解之后得到了肟醚类氨基甲酰甲胺3f-j。
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aminobenzaldehyde:氨基苯醛
aminoazonaphthalene氨基偶氮萘 | aminobenzaldehyde氨基苯醛 | aminobenzaldoxime氨基苯甲醛肟 氨基苯醛肟
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benzaldoxime:苯甲醛肟
benzaldehyde | 安息香醛, 苯甲醛 | benzaldoxime | 苯甲醛肟 | benzalin | 苯胺黑
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benzaldoxime:苯甲醛肟 苯醛肟
benzaldoxime 苯甲醛肟 苯醛肟 | benzalkonium 苯甲烃铵 苄烷铵 | benzalkoniumbromide 溴苄烷铵 溴苄烷铵 新洁尔灭 苯扎溴铵
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benzaldoxime; benzaldehyde oxime:苯甲醛肟
苯甲醛邻甲酸 benzaldehyde-o-carboxylic acid | 苯甲醛肟 benzaldoxime; benzaldehyde oxime | 苯甲醛肟甲[酸]酐 benzaldoximecarboxylic anhydride
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benzalethylamine:亚苄基乙基胺;N-亚苄乙胺
苯甲醛肟 benzaldoxime; benzaldehyde oxime | 苯甲醛肟甲[酸]酐 benzaldoximecarboxylic anhydride | 亚苄基乙基胺;N-亚苄乙胺 benzalethylamine
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formaldehyde oxime; formaldoxime:甲醛肟
二丙醇缩甲醛;二丙氧甲烷 formaldehyde dipropyl acetal; dipropoxymethane | 甲醛肟 formaldehyde oxime; formaldoxime | 甲醛苯腙 formaldehyde phenylhydrazone
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formaldehyde phenylhydrazone:甲醛苯腙
甲醛肟 formaldehyde oxime; formaldoxime | 甲醛苯腙 formaldehyde phenylhydrazone | 甲醛亚硫酸氢钠 formaldehyde sodium bisulfite