71940-33-5Relevant articles and documents
Assembling Porphyrins into Extended Network Structures by Employing Aromatic Dicarboxylates: Synthesis, Metal Exchange, and Heterogeneous Catalytic Studies
Dutta, Gargi,Jana, Ajay Kumar,Natarajan, Srinivasan
supporting information, p. 8932 - 8940 (2017/07/11)
Three new metal–organic porphyrinic framework compounds of zinc and 5,10,15,20-tetrakis(4-pyridyl)porphyrin (TPyP) have been synthesized under solvothermal conditions. The compounds [Zn5(C40H24N8)(C8H4O4)2(NO3)6(DMA)2] (DMA)3(H2O)8 (1; DMA=dimethylacetamide), [Zn3(C40H24N8)(C8H4O4)2(DMF)](DMF)5(H2O)12 (2), and [Zn3(C40H24N8)(C12H6O4)2(DMA)2](H2O)7 (3) have two (1) and three dimensionally (2 and 3) extended structures. All the three structures contain porphyrinic units connected through the carboxylate linkers. The nitrates bind the metal centers and are not hydrogen bonded. The different binding modes of nitrate in the structure of 1 are observed for the first time in a porphyrin-based MOF. The openness of the structure allowed us to explore metal exchange through a room-temperature metathetic route. Compound 2 undergoes 100 % exchange with copper, whereas compound 3 exchanges 70 % with copper. The copper-exchanged compounds Cu∈2 and Cu∈3 were observed to be good heterogeneous catalysts for many important organic reactions. The chemo and regioselective enamination of β-ketoesters, preparation of propargylamine derivatives as well as regioselective cycloadditions of alkyne and azide (click reactions) have been carried out with good yields and selectivity. All the compounds have been characterized by PXRD, IR, UV/Vis, atomic absorption spectroscopy (AAS), and energy-dispersive X-ray spectroscopy (for Cu exchange).
A new copper-based metal-organic framework as a promising heterogeneous catalyst for chemo- and regio-selective enamination of β-ketoesters
Zhao, Ying,Deng, Dong-Sheng,Ma, Lu-Fang,Ji, Bao-Ming,Wang, Li-Ya
supporting information, p. 10299 - 10301 (2013/10/22)
Assembly of 5-nitro-1,2,3-benzenetricarboxylic acid (H3nbta) with CuII in the presence of 1,3-bis(1,2,4-triazol-1-yl)propane (1,3-btp) leads to a new metal-organic framework, [Cu(Hnbta)(1,3-btp)] ·2H2O (A1), which is shown to be an efficient and recyclable heterogeneous catalyst for enamination of β-ketoesters with excellent product yields and selectivity.
On the Knorr synthesis of 6-bromo-4-methylquinolin-2(1H)-one
Wlodarczyk, Nicolas,Simenel, Catherine,Delepierre, Muriel,Barale, Jean-Christophe,Janin, Yves L.
scheme or table, p. 934 - 942 (2011/05/05)
In the course of our work on infectious diseases, we were led to prepare 6-bromo-2-chloro-4-methylquinoline as a starting material. Since surprisingly little has been reported in the literature, the two synthetic steps to this compound were investigated. The synthesis involves a condensation between -keto esters and 4-bromoaniline and the cyclization of the resulting anilides into 6-bromoquinolin-2(1H)-one, otherwise known as the Knorr reaction. The 1H NMR monitoring of the first step allowed us to optimize the conditions leading specifically to the anilide without the occurrence of the alternative crotonate. To illustrate the scope of our finding, few additional anilides featuring electron-attracting groups were prepared. The study of their cyclization revealed some unsuspected steric effect governing this second step. Aside from rectifying a few claims in this chemistry, this study led to a three-step preparation of 6-bromo-2-chloro-4-methylquinoline in 48% overall yield from 4-bromoaniline. Georg Thieme Verlag Stuttgart - New York.
