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Rationalization of Benzazole-2-carboxylate versus Benzazine-3-one/Benzazine-2,3-dione Selectivity Switch during Cyclocondensation of 2-Aminothiophenols/Phenols/Anilines with 1,2-Biselectrophiles in Aqueous Medium
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2017-09-15 00:00:00 , DOI: 10.1021/acs.joc.7b01548 Tejas M. Dhameliya 1 , Sumit S. Chourasiya 1 , Eshan Mishra 1 , Pradeep S. Jadhavar 1 , Prasad V. Bharatam 1 , Asit K. Chakraborti 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2017-09-15 00:00:00 , DOI: 10.1021/acs.joc.7b01548 Tejas M. Dhameliya 1 , Sumit S. Chourasiya 1 , Eshan Mishra 1 , Pradeep S. Jadhavar 1 , Prasad V. Bharatam 1 , Asit K. Chakraborti 1
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The cyclocondensation reaction of 2-aminothiophenols with 1,2-biselectrophiles such as ethyl glyoxalate and diethyl oxalate in aqueous medium leads to the formation of benzothiazole-2-carboxylates via the 5-endo-trig process contrary to Baldwin’s rule. On the other hand, the reaction of 2-aminophenols/anilines produced the corresponding benzazine-3-ones or benzazine-2,3-diones via the 6-exo-trig process in compliance with Baldwin’s rule. The mechanistic insights of these cyclocondensation reactions using the hard–soft acid–base principle, quantum chemical calculations (density functional theory), and orbital interaction studies rationalize the selectivity switch of benzothiazole-2-carboxylates versus benzazine-3-ones/benzazine-2,3-diones. The presence of water facilitates these cyclocondensation reactions by lowering of the energy barrier.
中文翻译：
在水介质中2-氨基苯硫酚/苯酚/苯胺与1,2-双亲电子试剂的环缩合反应中苯并-2-羧酸酯与苯并3-酮/苯并-2,3-二酮选择性开关的合理化
的2-氨基苯硫酚与1,2- biselectrophiles如乙醛酸乙酯和草酸二乙酯在水性介质中的引线经由5-形成苯并噻唑-2-羧酸酯的环化缩合反应内切- trig的过程相反Baldwin的规则。另一方面，2-氨基苯酚/苯胺的反应通过6- exo - trig生成了相应的benzazine-3-ones或benzazine-2,3-diones。符合鲍德温规则的流程。使用硬-软酸碱原理，量子化学计算（密度泛函理论）和轨道相互作用研究对这些环缩合反应的机理进行了深入研究，从而使苯并噻唑-2-羧酸酯与苯并三嗪-3-ones / benzazine-2的选择性转换合理化。 ，3-二酮。水的存在通过降低能垒来促进这些环缩合反应。
更新日期：2017-09-15
中文翻译：
在水介质中2-氨基苯硫酚/苯酚/苯胺与1,2-双亲电子试剂的环缩合反应中苯并-2-羧酸酯与苯并3-酮/苯并-2,3-二酮选择性开关的合理化
的2-氨基苯硫酚与1,2- biselectrophiles如乙醛酸乙酯和草酸二乙酯在水性介质中的引线经由5-形成苯并噻唑-2-羧酸酯的环化缩合反应内切- trig的过程相反Baldwin的规则。另一方面，2-氨基苯酚/苯胺的反应通过6- exo - trig生成了相应的benzazine-3-ones或benzazine-2,3-diones。符合鲍德温规则的流程。使用硬-软酸碱原理，量子化学计算（密度泛函理论）和轨道相互作用研究对这些环缩合反应的机理进行了深入研究，从而使苯并噻唑-2-羧酸酯与苯并三嗪-3-ones / benzazine-2的选择性转换合理化。 ，3-二酮。水的存在通过降低能垒来促进这些环缩合反应。
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