亚磺化脱卤反应在含氟卟啉合成及转化中的应用
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摘要
本论文的主要内容是发展合成含氟卟啉的新方法,并对所得到的氟烷基卟啉的转化进行研究。我们以全氟碘代烷和易得的卟啉为原料,通过亚磺化脱卤反应将氟烷基引入卟啉,并研究了亚磺化脱卤反应在氟烷基卟啉中的应用。本论文分五章。
第一章,绪论。
第二章,5,10,15-三芳基卟啉的氟烷基化反应研究。本章研究了在亚磺化脱卤反应条件下5,10,15-三芳基卟啉的氟烷基化反应,并对反应条件进行了优化。在优化条件(原料比例为5,10,15-三芳基卟啉/多氟碘代烷RFI/Na2S2O4/NaHCO3=1/3/4.5/4.5,DMSO/CH2Cl2(vol/vol=1/1)为混和溶剂,温度为65℃左右的回流温度)下进行反应,得到了2-全氟烷基-5,10,15-三芳基卟啉和5,10,15-三芳基-20-全氟烷基卟啉。从两种产物的比例可以看出卟啉meso-位的反应活性要高于卟啉β-位的反应活性。
第三章,2-和20-全氟烷基-5,10,15-三芳基卟啉自由基的分子内环化反应研究。1,3-二碘六氟丙烷与5,10,15-三芳基卟啉在DMSO/CH2Cl2(vol/vol=1/1)的混和溶剂中,在Na2S2O4/NaCO3的存在下反应(原料比例为5,10,15-三芳基卟啉/多氟碘代烷RFI/Na2S2O4/NaHCO3=1/1.5/4.5/4.5),得到meso-与β-位全氟丙烷相连的六元分子内环化产物2,20-六氟丙烷基-5,10,15-三芳基卟啉,并证明2-和20-(3-碘六氟丙烷基)-5,10,15-三芳基卟啉是该反应的中间体。以2-或20-(2-氯四氟乙烷基)-5,10,15-三苯基锌卟啉为原料,改变反应条件,卟啉:保险粉:碳酸氢钠=1:10:10,直接以DMSO为溶剂,反应温度升高到100℃,2-或20-(2-氯四氟乙烷基)-5,10,15-三苯基锌卟啉能发生C-Cl键的断裂而顺利的进行了分子内环化反应,得到meso-与β-位全氟丙烷相连的五元分子内环化产物2,20-四氟乙烷基-5,10,15-三苯基卟啉。2,20-六氟丙烷基-5,10,15-三芳基锌卟啉和2,20-四氟乙烷基-5,10,15-三苯基锌卟啉在硅胶的催化下可以发生水解反应生成5,10,15-三芳基-2,20-(20’-羰基)-四氟丙烷基锌卟啉和5,10,15-三苯基-2,20-(20’-羰基)-二氟乙烷基锌卟啉。而自由碱卟啉在同样条件下不能发生水解反应。
第四章,5,15-全氟烷基-10,20-二苯基卟啉自由基的产生及它们的分子内环化反应。不同比例的1,3-二碘六氟丙烷与5,15-二苯基卟啉在亚磺化脱卤的条件下反应,可以得到三种不同类型的反应产物,他们分别为单取代产物2-(3-碘六氟丙烷基)-5,15-二苯基卟啉和5,15-二苯基-10-(3-碘六氟丙烷基)卟啉、单环化产物5,15-二苯基-2,20-六氟丙烷基卟啉和双环化产物5,15-二苯基-2,20:10,12-二(六氟丙烷基)卟啉。在双环化反应中,若不加碱,即得到5,15-二苯基-2,20:10,12-二(六氟丙烷基)卟啉和5,15-二苯基-2,20:8,10-二(六氟丙烷基)卟啉的混合物。我们利用活化全氟烷基中C-Cl键的方法,5-(2-氯四氟乙基)-10,20-二苯基锌卟啉和5,15-二(2-氯四氟乙基)-10,20-二苯基锌卟啉也可以发生分子内环化反应,分别得到单环化产物与双环化产物。
第五章,5,15-二丙基卟啉的氟烷基化反应研究。用5,15-二丙基卟啉代替5,15-二苯基卟啉进行氟烷基化反应,在单取代反应和单环化反应条件下,二者并没有明显区别,在双取代反应条件下,在亚磺化脱卤体系中,若不加NaHCO3时,得到5-三氟乙烯基-10,20-二丙烷基卟啉,而当NaHCO3存在时,得到meso,meso-位相连的双-(5-多氟烷基-5,15-二氢-10,20-二丙烷基二氢卟啉)。
The dissertation focused on the development of new method for the synthesis of fluoroalkylated porphyrins. Fluoroalkyl group was introduced to porphyrins by sulfinatodehalogenation system. We also studied the application of sulfinatodehalogenation on the fluoroalkylated porphyrins. The dissertation consisted of five chapters.
ChapterⅠ. Introduction.
ChapterⅡ. Fluoroalkylation of 5,10,15-triarylporphyrins. We investigated fluoroalkylation of 5,10,15-triarylporphyrins with fluoroalkyl halides by sulfinatodehalogenation system. Treatment of 5,10,15-triarylporphyrins with perfluoroalkyl iodides RFI in the presence of Na2S2O4/NaHCO3(molar ratio 1:3:4.5:4.5) in DMSO /CH2Cl2(V/V, 1/1) at 65℃for 3h, gave 2-perfluoroalkyl-5,10,15-triarylporphyrins and 5,10,15-triaryl-20-perfluoroalkylporphyrins. The ratio of the products show that the activity of the meso-position of porphyrins is higher than that of theβ-position of porphyrins.
ChapterⅢ. Intramolecular cyclizations of 2- and 20-perfluoroalkyl-5,10,15-triarylporphyrin radicals. When 1,3-diiodohexafluoropropane was subjected to react with 5,10,15-triarylporphyrins, in the presence of Na2S2O4/NaHCO3 (reactant ratio = 1:1.5:4.5:4.5) in DMSO/CH2Cl2(v/v=1/1) at 65℃for 8h, 5,10,15-triaryl-2,20-(hexafluoropropanediyl)porphyrins was obtained. It was found that the intermediates of this reaction are 2-(3-iodohexafluoroalkyl)-5,10,15-triarylporphyrin and 20-(3-iodohexafluoroalkyl)-5,10,15-triarylporphyrin. Because the carbon-chlorine bond of perfluoroalkyl chlorides can be activated in sulfinatodehalogenation system in DMSO at higher temperature, the chlorine atoms of 2-(2-Chlorotetrafluoroethyl)-5,10,15-triphenylporphinato zinc(Ⅱ) and 5,10,15-triphenyl-20-(2-Chlorotetrafluoroethyl)porphinato zinc (Ⅱ) could be homogenously cleaved by Na2S2O4/NaHCO3(reactant ratio=1:10:10) in DMSO at 100℃. Both theβ- tetrafluoroethyl and meso- tetrafluoroethyl radicals produced launch their intramolecular cyclization at respective meso- andβ-positions giving a single fluorinated fused porphyrin, ie. 5,10,15-triphenyl-2,20-(tetrafluoroethanediyl)porphinato zinc(Ⅱ). The hydrolysis of CF2 moiety may be simply accomplished by treating 5,10,15-triaryl-2,20-(hexafluoropropanediyl) porphinato zinc (Ⅱ) (or 5,10,15-triphenyl-2,20-(tetrafluoroethanediyl)porphinato zinc(Ⅱ)) with silica gel at room temperature.
ChapterⅣ. Generation of 5,15-perfluoroalkyl-10,20-diphenylporphyrin radicals and their intramolecular cyclizations. Heating 5,15-diphenylporphyrin with 1,3-diiodohexafluoropropane in the presence of Na2S2O4/NaHCO3 in the different molar ratios of material in DMSO-CH2Cl2 (v/v, 1/1) at 65℃yielded three different products. They are a mixture of a mono fluoroalkylated porphyrins (the mixture of 2-(3-iodohexafluoropropyl)-5,15-diphenylporphyrin and 5, 15-diphenyl-10-(3-iodohexafluoropropyl)porphyrin), a mono fluoroalkylated meso,β-fused porphyrin (5,15-diphenyl-2,20-(hexafluoropropanediyl)porphyrins)and a double fluoroalkylated meso,β-fused porphyrin(5,15-diphenyl-2,20:10,12-di(hexafluoropropanediyl)porphyrins). In the absence of NaHCO3, the products were the mixture of 5,15-diphenyl-2,20:10,12-di(hexafluoropropanediyl)porphyrins and 5,15-diphenyl-2,20:8,10-di(hexafluoropropanediyl)porphyrins. Using activation method of C-Cl bonds in perfluoroalkyl chlorides, the mono cyclization of 5-(2- Chlorotetrafluoroethyl)-10,20-diphenylporphyrin and the double cyclization of 5, 15-di(2- Chlorotetrafluoroethyl) -10,20- diphenylporphyrin could also take place.
ChapterⅤ. Fluoroalkylation of 5, 15-dipropylporphyrin. Using 5, 15-dipropylporphyrin as the starting material instead of 5,15-diphenylporphyrin, the results were quite similar for the mono fluoroalkylated and the mono cyclization reaction. But for the double fluoroalkylated reactions, in the absence of NaHCO3, the product was 5-(1,2,2-trifluorovinyl)-10,20- dipropylporphyrin; in the presence of NaHCO3, the product was meso,meso-linked bis-(5-perfluoroalkyl-5,15-dihydro-10,20-dipropylporphodimethene).
第一章,绪论。
第二章,5,10,15-三芳基卟啉的氟烷基化反应研究。本章研究了在亚磺化脱卤反应条件下5,10,15-三芳基卟啉的氟烷基化反应,并对反应条件进行了优化。在优化条件(原料比例为5,10,15-三芳基卟啉/多氟碘代烷RFI/Na2S2O4/NaHCO3=1/3/4.5/4.5,DMSO/CH2Cl2(vol/vol=1/1)为混和溶剂,温度为65℃左右的回流温度)下进行反应,得到了2-全氟烷基-5,10,15-三芳基卟啉和5,10,15-三芳基-20-全氟烷基卟啉。从两种产物的比例可以看出卟啉meso-位的反应活性要高于卟啉β-位的反应活性。
第三章,2-和20-全氟烷基-5,10,15-三芳基卟啉自由基的分子内环化反应研究。1,3-二碘六氟丙烷与5,10,15-三芳基卟啉在DMSO/CH2Cl2(vol/vol=1/1)的混和溶剂中,在Na2S2O4/NaCO3的存在下反应(原料比例为5,10,15-三芳基卟啉/多氟碘代烷RFI/Na2S2O4/NaHCO3=1/1.5/4.5/4.5),得到meso-与β-位全氟丙烷相连的六元分子内环化产物2,20-六氟丙烷基-5,10,15-三芳基卟啉,并证明2-和20-(3-碘六氟丙烷基)-5,10,15-三芳基卟啉是该反应的中间体。以2-或20-(2-氯四氟乙烷基)-5,10,15-三苯基锌卟啉为原料,改变反应条件,卟啉:保险粉:碳酸氢钠=1:10:10,直接以DMSO为溶剂,反应温度升高到100℃,2-或20-(2-氯四氟乙烷基)-5,10,15-三苯基锌卟啉能发生C-Cl键的断裂而顺利的进行了分子内环化反应,得到meso-与β-位全氟丙烷相连的五元分子内环化产物2,20-四氟乙烷基-5,10,15-三苯基卟啉。2,20-六氟丙烷基-5,10,15-三芳基锌卟啉和2,20-四氟乙烷基-5,10,15-三苯基锌卟啉在硅胶的催化下可以发生水解反应生成5,10,15-三芳基-2,20-(20’-羰基)-四氟丙烷基锌卟啉和5,10,15-三苯基-2,20-(20’-羰基)-二氟乙烷基锌卟啉。而自由碱卟啉在同样条件下不能发生水解反应。
第四章,5,15-全氟烷基-10,20-二苯基卟啉自由基的产生及它们的分子内环化反应。不同比例的1,3-二碘六氟丙烷与5,15-二苯基卟啉在亚磺化脱卤的条件下反应,可以得到三种不同类型的反应产物,他们分别为单取代产物2-(3-碘六氟丙烷基)-5,15-二苯基卟啉和5,15-二苯基-10-(3-碘六氟丙烷基)卟啉、单环化产物5,15-二苯基-2,20-六氟丙烷基卟啉和双环化产物5,15-二苯基-2,20:10,12-二(六氟丙烷基)卟啉。在双环化反应中,若不加碱,即得到5,15-二苯基-2,20:10,12-二(六氟丙烷基)卟啉和5,15-二苯基-2,20:8,10-二(六氟丙烷基)卟啉的混合物。我们利用活化全氟烷基中C-Cl键的方法,5-(2-氯四氟乙基)-10,20-二苯基锌卟啉和5,15-二(2-氯四氟乙基)-10,20-二苯基锌卟啉也可以发生分子内环化反应,分别得到单环化产物与双环化产物。
第五章,5,15-二丙基卟啉的氟烷基化反应研究。用5,15-二丙基卟啉代替5,15-二苯基卟啉进行氟烷基化反应,在单取代反应和单环化反应条件下,二者并没有明显区别,在双取代反应条件下,在亚磺化脱卤体系中,若不加NaHCO3时,得到5-三氟乙烯基-10,20-二丙烷基卟啉,而当NaHCO3存在时,得到meso,meso-位相连的双-(5-多氟烷基-5,15-二氢-10,20-二丙烷基二氢卟啉)。
The dissertation focused on the development of new method for the synthesis of fluoroalkylated porphyrins. Fluoroalkyl group was introduced to porphyrins by sulfinatodehalogenation system. We also studied the application of sulfinatodehalogenation on the fluoroalkylated porphyrins. The dissertation consisted of five chapters.
ChapterⅠ. Introduction.
ChapterⅡ. Fluoroalkylation of 5,10,15-triarylporphyrins. We investigated fluoroalkylation of 5,10,15-triarylporphyrins with fluoroalkyl halides by sulfinatodehalogenation system. Treatment of 5,10,15-triarylporphyrins with perfluoroalkyl iodides RFI in the presence of Na2S2O4/NaHCO3(molar ratio 1:3:4.5:4.5) in DMSO /CH2Cl2(V/V, 1/1) at 65℃for 3h, gave 2-perfluoroalkyl-5,10,15-triarylporphyrins and 5,10,15-triaryl-20-perfluoroalkylporphyrins. The ratio of the products show that the activity of the meso-position of porphyrins is higher than that of theβ-position of porphyrins.
ChapterⅢ. Intramolecular cyclizations of 2- and 20-perfluoroalkyl-5,10,15-triarylporphyrin radicals. When 1,3-diiodohexafluoropropane was subjected to react with 5,10,15-triarylporphyrins, in the presence of Na2S2O4/NaHCO3 (reactant ratio = 1:1.5:4.5:4.5) in DMSO/CH2Cl2(v/v=1/1) at 65℃for 8h, 5,10,15-triaryl-2,20-(hexafluoropropanediyl)porphyrins was obtained. It was found that the intermediates of this reaction are 2-(3-iodohexafluoroalkyl)-5,10,15-triarylporphyrin and 20-(3-iodohexafluoroalkyl)-5,10,15-triarylporphyrin. Because the carbon-chlorine bond of perfluoroalkyl chlorides can be activated in sulfinatodehalogenation system in DMSO at higher temperature, the chlorine atoms of 2-(2-Chlorotetrafluoroethyl)-5,10,15-triphenylporphinato zinc(Ⅱ) and 5,10,15-triphenyl-20-(2-Chlorotetrafluoroethyl)porphinato zinc (Ⅱ) could be homogenously cleaved by Na2S2O4/NaHCO3(reactant ratio=1:10:10) in DMSO at 100℃. Both theβ- tetrafluoroethyl and meso- tetrafluoroethyl radicals produced launch their intramolecular cyclization at respective meso- andβ-positions giving a single fluorinated fused porphyrin, ie. 5,10,15-triphenyl-2,20-(tetrafluoroethanediyl)porphinato zinc(Ⅱ). The hydrolysis of CF2 moiety may be simply accomplished by treating 5,10,15-triaryl-2,20-(hexafluoropropanediyl) porphinato zinc (Ⅱ) (or 5,10,15-triphenyl-2,20-(tetrafluoroethanediyl)porphinato zinc(Ⅱ)) with silica gel at room temperature.
ChapterⅣ. Generation of 5,15-perfluoroalkyl-10,20-diphenylporphyrin radicals and their intramolecular cyclizations. Heating 5,15-diphenylporphyrin with 1,3-diiodohexafluoropropane in the presence of Na2S2O4/NaHCO3 in the different molar ratios of material in DMSO-CH2Cl2 (v/v, 1/1) at 65℃yielded three different products. They are a mixture of a mono fluoroalkylated porphyrins (the mixture of 2-(3-iodohexafluoropropyl)-5,15-diphenylporphyrin and 5, 15-diphenyl-10-(3-iodohexafluoropropyl)porphyrin), a mono fluoroalkylated meso,β-fused porphyrin (5,15-diphenyl-2,20-(hexafluoropropanediyl)porphyrins)and a double fluoroalkylated meso,β-fused porphyrin(5,15-diphenyl-2,20:10,12-di(hexafluoropropanediyl)porphyrins). In the absence of NaHCO3, the products were the mixture of 5,15-diphenyl-2,20:10,12-di(hexafluoropropanediyl)porphyrins and 5,15-diphenyl-2,20:8,10-di(hexafluoropropanediyl)porphyrins. Using activation method of C-Cl bonds in perfluoroalkyl chlorides, the mono cyclization of 5-(2- Chlorotetrafluoroethyl)-10,20-diphenylporphyrin and the double cyclization of 5, 15-di(2- Chlorotetrafluoroethyl) -10,20- diphenylporphyrin could also take place.
ChapterⅤ. Fluoroalkylation of 5, 15-dipropylporphyrin. Using 5, 15-dipropylporphyrin as the starting material instead of 5,15-diphenylporphyrin, the results were quite similar for the mono fluoroalkylated and the mono cyclization reaction. But for the double fluoroalkylated reactions, in the absence of NaHCO3, the product was 5-(1,2,2-trifluorovinyl)-10,20- dipropylporphyrin; in the presence of NaHCO3, the product was meso,meso-linked bis-(5-perfluoroalkyl-5,15-dihydro-10,20-dipropylporphodimethene).
引文
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