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聚（吡唑基）苯基甲烷配体的无溶剂合成及三（3,5-二甲基吡唑-1-基）苯基甲烷的热转化

Solventless Synthesis of Poly(pyrazolyl)phenyl-methane Ligands and Thermal Transformation of Tris(3,5-dimethylpyrazol-1-yl)phenylmethane.

作者信息

Rodríguez-Venegas Edith, García-Báez Efrén V, Martínez-Martínez Francisco J, Cruz Alejandro, Padilla-Martínez Itzia I

机构信息

Laboratorio de Química Supramolecular y Nanociencias, Instituto Politécnico Nacional-UPIBI, Av. Acueducto s/n Barrio la Laguna Ticomán, Ciudad de México C.P. 07340, Mexico.

Facultad de Ciencias Químicas, Universidad de Colima, Km. 9 Carretera Colima-Coquimatlán, Coquimatlán C.P. 28400, Mexico.

出版信息

Molecules. 2017 Mar 11;22(3):441. doi: 10.3390/molecules22030441.

DOI:10.3390/molecules22030441
PMID:28287474
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6155200/
Abstract

The solventless synthesis of tris(pyrazolyl)phenylmethane ligands of formula C₆H₅C(Pz)₃ (R = H, Me), starting from PhCCl₃ and 3,5-dimethylpyrazole (Pz) or pyrazole (Pz) was performed. The sterically crowded C₆H₅C(Pz)₃ is thermally transformed into the bis(pyrazolyl)(-pyrazolyl)phenylmethane ligand Pz-C₆H₄CH(Pz)₂. In this compound both Pz rings are linked through the N-atom to the methine C-atom. At higher temperatures, the binding mode of Pz changes from N1 to C4. All transformations occurred via quinonoid carbocation intermediates that undergo an aromatic electrophilic substitution on the 4-position of Pz. Reaction conditions were established to obtain five tris(pyrazolyl)phenylmethane ligands in moderate to good yields. ¹H- and C-NMR spectroscopy and X-ray diffraction of single crystals support the proposed structures.

摘要

以三氯甲苯（PhCCl₃）和3,5 - 二甲基吡唑（Pz）或吡唑（Pz）为原料，进行了式为C₆H₅C(Pz)₃（R = H，Me）的三（吡唑基）苯基甲烷配体的无溶剂合成。空间位阻较大的C₆H₅C(Pz)₃热转化为双（吡唑基）（-吡唑基）苯基甲烷配体Pz-C₆H₄CH(Pz)₂。在该化合物中，两个Pz环均通过N原子与次甲基C原子相连。在较高温度下，Pz的结合模式从N1变为C4。所有转化均通过醌型碳正离子中间体进行，该中间体在Pz的4位发生芳香亲电取代反应。建立了反应条件，以中等至良好的产率获得了五种三（吡唑基）苯基甲烷配体。单晶的¹H和¹³C核磁共振光谱以及X射线衍射证实了所提出的结构。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/000fad524eb5/molecules-22-00441-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/6026959467c7/molecules-22-00441-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/1b929d81065b/molecules-22-00441-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/080232068ab4/molecules-22-00441-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/1fa998b36f5a/molecules-22-00441-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/c21c3f942466/molecules-22-00441-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/8200dc43bcce/molecules-22-00441-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/d03570775453/molecules-22-00441-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/e7b00bf0c65b/molecules-22-00441-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/000fad524eb5/molecules-22-00441-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/6026959467c7/molecules-22-00441-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/1b929d81065b/molecules-22-00441-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/080232068ab4/molecules-22-00441-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/1fa998b36f5a/molecules-22-00441-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/c21c3f942466/molecules-22-00441-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/8200dc43bcce/molecules-22-00441-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/d03570775453/molecules-22-00441-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/e7b00bf0c65b/molecules-22-00441-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7da2/6155200/000fad524eb5/molecules-22-00441-g005.jpg

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