当前位置：
X-MOL 学术
›
Catal. Sci. Technol.
›
论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Simple low cost porphyrinic photosensitizers for large scale chemoselective oxidation of sulfides to sulfoxides under green conditions: targeted protonation of porphyrins†
Catalysis Science & Technology ( IF 5 ) Pub Date : 2017-12-18 00:00:00 , DOI: 10.1039/c7cy02308a Aida G. Mojarrad 1, 2, 3, 4 , Saeed Zakavi 1, 2, 3, 4
Catalysis Science & Technology ( IF 5 ) Pub Date : 2017-12-18 00:00:00 , DOI: 10.1039/c7cy02308a Aida G. Mojarrad 1, 2, 3, 4 , Saeed Zakavi 1, 2, 3, 4
Affiliation
|
Aerobic photooxidation of sulfides with the diacids of meso-tetra(phenyl)porphyrin, H2TPP (acid = CF3COOH, Cl2CHCOOH, HClO4 and H2SO4) under sunlight in acetonitrile gave the corresponding sulfoxides as nearly the exclusive product. The photocatalytic activity of the dications decreased as H4TPP(ClO4)2 ≫ H4TPP(Cl2CHCOO)2 ≫ H4TPP(CF3COO)2 > H4TPP(HSO4)2. Also, H4TPP(ClO4)2 and H4TPP(Cl2CHCOO)2 showed a remarkably increased oxidative stability in comparison with the free base porphyrin. The singlet oxygen quantum yield (φΔ) of the porphyrin diacids was found to be dependent on the acid used for the protonation of H2TPP. The solvent effect on the efficiency of the oxidation reaction was investigated using acetonitrile, 1,2-dichloroethane (DCE) and toluene. The higher conversions achieved in acetonitrile and DCE are in accord with the higher singlet oxygen lifetime in these solvents. Also, the lower fluorescence quantum yield of porphyrin dications in acetonitrile relative to that in DCE was used to explain the higher efficiency of the former. The porphyrin diacids can also accelerate the oxidation reaction through an acid catalysis mechanism. Also, cooxidation of methyl phenyl sulfide and diphenyl sulfide was conducted to provide insights into the nature of the active intermediates involved in the oxidation of sulfides to sulfoxides and partial overoxidation of the sulfoxides to sulfones. The results showed much higher reactivity of the persulfoxide intermediate compared to that of singlet oxygen. The catalytic system was successfully employed to the large scale preparation of sulfoxides from the corresponding sulfides under mild conditions.
中文翻译：
简单的低成本卟啉光敏剂，用于在绿色条件下将硫化物大规模化学选择性氧化为亚砜：卟啉的目标质子化†
用的二元酸硫化物的需氧光氧化内消旋-四（苯基）卟啉，H 2 TPP（酸= CF 3 COOH，氯2 CHCOOH，高氯酸4和H 2 SO 4）下于乙腈阳光，得到相应的亚砜，近异产品。的双阳离子的光催化活性降低以H 4 TPP（CLO 4）2 »ħ 4 TPP（CL 2 CHCOO）2 »ħ 4 TPP（CF 3 COO）2 > H ^ 4 TPP（HSO 4）2。而且，与游离碱卟啉相比，H 4 TPP（ClO 4）2和H 4 TPP（Cl 2 CHCOO）2显示出显着增加的氧化稳定性。单线态氧量子产率（φ Δ卟啉二酸的）被认为是取决于用于H的质子化的酸2TPP。使用乙腈，1,2-二氯乙烷（DCE）和甲苯研究了溶剂对氧化反应效率的影响。在乙腈和DCE中获得的更高转化率与这些溶剂中更高的单线态氧寿命相一致。同样，相对于DCE，卟啉指示剂在乙腈中的荧光量子产率较低，这可以解释前者的较高效率。卟啉二酸还可以通过酸催化机理来加速氧化反应。另外，进行了甲基苯硫醚和二苯硫醚的共氧化，以提供有关硫化物氧化为亚砜和亚砜部分过氧化为砜的活性中间体的性质的见解。结果表明，与单线态氧相比，过亚砜中间体的反应性更高。该催化体系已成功地用于在温和条件下从相应的硫化物大规模制备亚砜。
更新日期：2017-12-18
中文翻译：
简单的低成本卟啉光敏剂，用于在绿色条件下将硫化物大规模化学选择性氧化为亚砜：卟啉的目标质子化†
用的二元酸硫化物的需氧光氧化内消旋-四（苯基）卟啉，H 2 TPP（酸= CF 3 COOH，氯2 CHCOOH，高氯酸4和H 2 SO 4）下于乙腈阳光，得到相应的亚砜，近异产品。的双阳离子的光催化活性降低以H 4 TPP（CLO 4）2 »ħ 4 TPP（CL 2 CHCOO）2 »ħ 4 TPP（CF 3 COO）2 > H ^ 4 TPP（HSO 4）2。而且，与游离碱卟啉相比，H 4 TPP（ClO 4）2和H 4 TPP（Cl 2 CHCOO）2显示出显着增加的氧化稳定性。单线态氧量子产率（φ Δ卟啉二酸的）被认为是取决于用于H的质子化的酸2TPP。使用乙腈，1,2-二氯乙烷（DCE）和甲苯研究了溶剂对氧化反应效率的影响。在乙腈和DCE中获得的更高转化率与这些溶剂中更高的单线态氧寿命相一致。同样，相对于DCE，卟啉指示剂在乙腈中的荧光量子产率较低，这可以解释前者的较高效率。卟啉二酸还可以通过酸催化机理来加速氧化反应。另外，进行了甲基苯硫醚和二苯硫醚的共氧化，以提供有关硫化物氧化为亚砜和亚砜部分过氧化为砜的活性中间体的性质的见解。结果表明，与单线态氧相比，过亚砜中间体的反应性更高。该催化体系已成功地用于在温和条件下从相应的硫化物大规模制备亚砜。
京公网安备 11010802027423号