Stepwise Formation of 1,3-Diazolium-4-thiolates by M眉nchnone Cycloadditions: Promising Candidates for Nonlinear Optics
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- 作者：David Cantillo ; Mart铆n 脕valos ; Reyes Babiano ; Pedro Cintas ; Jos茅 L. Jim茅nez ; Mark E. Light ; Juan C. Palacios ; Roc铆o Porro
- 刊名：Journal of Organic Chemistry
- 出版年：2014
- 出版时间：May 2, 2014
- 年：2014
- 卷：79
- 期：9
- 页码：4201-4205
- 全文大小：280K
- 年卷期：v.79,no.9(May 2, 2014)
- ISSN：1520-6904
文摘
An improved preparation of mesoionic heterocycles 1,3-diazolium-4-thiolates by [3 + 2] cycloadditions of m眉nchnones with aryl isothiocyanates is reported. The process takes place with high or complete regioselectivity, and fast and clean transformations are observed under microwave heating in DMF. DFT calculations support that this cycloaddition proceeds preferably through a stepwise mechanism. Given the pattern substitution around the mesoionic ring resulting in a push鈥損ull system, theoretical estimations predict large hyperpolarizabilities in some cases, which is typical of molecules exhibiting nonlinear optical responses.