{"title":"通过在 β-吡咯碳原子上连续引入 1 至 6 个芳基,合成 β-芳基化三吡咯[2.1.1] 及其特性","authors":"Akrti Sharma, Mangalampalli Ravikanth","doi":"10.1016/j.tet.2024.134349","DOIUrl":null,"url":null,"abstract":"<div><div>The <em>β</em>-arylated <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrins[2.1.1] containing two, three, and four <em>p</em>-fluorophenyl groups were synthesized by reacting appropriate <em>β</em>-bromo triphyrin[2.1.1] with <em>p</em>-fluorophenyl boronic acid in toluene/THF/H<sub>2</sub>O (1:1:1) at 80 <sup>ο</sup>C for 8 h–12 h and their properties were compared with our previously reported <em>β</em>-arylated triphyrins[2.1.1] containing one and six <em>p</em>-fluorophenyl groups. The increase of the number of <em>p</em>-fluorophenyl groups at the <em>β</em>-pyrrole carbons induces steric hindrance at the periphery of triphyrin[2.1.1] that results in the alteration of electronic properties due to distortion in the macrocycle which is reflected in their structure, spectral and redox properties. The X-ray structure analysis revealed that <em>β</em>-di(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] was almost planar like <em>meso</em>-tetra(phenyl) triphyrin[2.1.1] whereas the <em>β</em>-hexa(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] was significantly distorted. The absorption spectra of <em>β</em>-arylated triphyrins[2.1.1] showed bathochromically shifted Soret and Q-bands with reduction in absorption coefficients and increase in the bandwidth compared to the <em>β</em>-unsubstituted <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] and the maximum effects were noted for <em>β</em>-hexa(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1]. The <em>β</em>-arylated <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrins[2.1.1] are stable under electrochemical conditions and DFT/TD-DFT studies are in agreement with the experimental observations.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134349"},"PeriodicalIF":2.1000,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis and properties of β-arylated triphyrins[2.1.1] by successive introduction of one to six aryl groups at the β-pyrrole carbons\",\"authors\":\"Akrti Sharma, Mangalampalli Ravikanth\",\"doi\":\"10.1016/j.tet.2024.134349\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The <em>β</em>-arylated <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrins[2.1.1] containing two, three, and four <em>p</em>-fluorophenyl groups were synthesized by reacting appropriate <em>β</em>-bromo triphyrin[2.1.1] with <em>p</em>-fluorophenyl boronic acid in toluene/THF/H<sub>2</sub>O (1:1:1) at 80 <sup>ο</sup>C for 8 h–12 h and their properties were compared with our previously reported <em>β</em>-arylated triphyrins[2.1.1] containing one and six <em>p</em>-fluorophenyl groups. The increase of the number of <em>p</em>-fluorophenyl groups at the <em>β</em>-pyrrole carbons induces steric hindrance at the periphery of triphyrin[2.1.1] that results in the alteration of electronic properties due to distortion in the macrocycle which is reflected in their structure, spectral and redox properties. The X-ray structure analysis revealed that <em>β</em>-di(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] was almost planar like <em>meso</em>-tetra(phenyl) triphyrin[2.1.1] whereas the <em>β</em>-hexa(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] was significantly distorted. The absorption spectra of <em>β</em>-arylated triphyrins[2.1.1] showed bathochromically shifted Soret and Q-bands with reduction in absorption coefficients and increase in the bandwidth compared to the <em>β</em>-unsubstituted <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1] and the maximum effects were noted for <em>β</em>-hexa(<em>p</em>-fluorophenyl) <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrin[2.1.1]. The <em>β</em>-arylated <em>meso</em>-tetra(<em>p</em>-tolyl) triphyrins[2.1.1] are stable under electrochemical conditions and DFT/TD-DFT studies are in agreement with the experimental observations.</div></div>\",\"PeriodicalId\":437,\"journal\":{\"name\":\"Tetrahedron\",\"volume\":\"168 \",\"pages\":\"Article 134349\"},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2024-10-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Tetrahedron\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0040402024005301\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Tetrahedron","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0040402024005301","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Synthesis and properties of β-arylated triphyrins[2.1.1] by successive introduction of one to six aryl groups at the β-pyrrole carbons
The β-arylated meso-tetra(p-tolyl) triphyrins[2.1.1] containing two, three, and four p-fluorophenyl groups were synthesized by reacting appropriate β-bromo triphyrin[2.1.1] with p-fluorophenyl boronic acid in toluene/THF/H2O (1:1:1) at 80 οC for 8 h–12 h and their properties were compared with our previously reported β-arylated triphyrins[2.1.1] containing one and six p-fluorophenyl groups. The increase of the number of p-fluorophenyl groups at the β-pyrrole carbons induces steric hindrance at the periphery of triphyrin[2.1.1] that results in the alteration of electronic properties due to distortion in the macrocycle which is reflected in their structure, spectral and redox properties. The X-ray structure analysis revealed that β-di(p-fluorophenyl) meso-tetra(p-tolyl) triphyrin[2.1.1] was almost planar like meso-tetra(phenyl) triphyrin[2.1.1] whereas the β-hexa(p-fluorophenyl) meso-tetra(p-tolyl) triphyrin[2.1.1] was significantly distorted. The absorption spectra of β-arylated triphyrins[2.1.1] showed bathochromically shifted Soret and Q-bands with reduction in absorption coefficients and increase in the bandwidth compared to the β-unsubstituted meso-tetra(p-tolyl) triphyrin[2.1.1] and the maximum effects were noted for β-hexa(p-fluorophenyl) meso-tetra(p-tolyl) triphyrin[2.1.1]. The β-arylated meso-tetra(p-tolyl) triphyrins[2.1.1] are stable under electrochemical conditions and DFT/TD-DFT studies are in agreement with the experimental observations.
期刊介绍:
Tetrahedron publishes full accounts of research having outstanding significance in the broad field of organic chemistry and its related disciplines, such as organic materials and bio-organic chemistry.
Regular papers in Tetrahedron are expected to represent detailed accounts of an original study having substantially greater scope and details than that found in a communication, as published in Tetrahedron Letters.
Tetrahedron also publishes thematic collections of papers as special issues and ''Reports'', commissioned in-depth reviews providing a comprehensive overview of a research area.