Thiophene ring-fragmentation reactions: Principles and scale-up towards NLO materials

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• 作者：Daniel Lumpi^a ; ^{daniel.lumpi@tuwien.ac.at} ; Johannes Steindl^a ; Sebastian Steiner^a ; Victor Carl^a ; Paul Kautny^a ; Michael Schö ; n^a ; Florian Glö ; cklhofer^a ; Brigitte Holzer^a ; Berthold Stö ; ger^b ; Ernst Horkel^a ; Christian Hametner^a ; Georg Reider^c ; Marko D. Mihovilovic^a ; Johannes Frö ; hlich^a
• 关键词：Thiophene ring-opening ; Reaction mechanism ; Reaction kinetics ; Inline monitoring ; Second harmonic generation
• 刊名：Tetrahedron
• 出版年：2017
• 出版时间：2 February 2017
• 年：2017
• 卷：73
• 期：5
• 页码：472-480
• 全文大小：1497 K
• 卷排序：73

文摘

A systematic study on the thiophene ring-fragmentation (TRF) reaction, yielding the Z-isomer of ene-yne type compounds, is presented. The investigations focus on the origins and pathways of potential side-reactions, resulting in an advanced synthetic protocol featuring enhanced selectivity and efficiency. The fragmentation threshold temperatures as well as reaction kinetics have been investigated utilizing inline infrared spectroscopy revealing unexpected results particularly concerning the reaction order (zero-order process). With regard to safety, selectivity, and up-scaling a flow-chemistry procedure for the TRF reaction has been developed. Finally, the technological relevance of the ene-yne structural motif is extended by a new design concept for NLO-chromophores showing the highest second harmonic generation efficiencies reported for these scaffolds.