Synthesis, experimental and theoretical studies on the factors influencing the pKa values of new crown ethers containing a diarylphosphinic acid unit

TETRAHEDRON

卷:72

Article

Szabo, Tamas¹  Dargo, Gergo^1,2  Szentjobi, Hajnalka¹  Toth, Tunde¹  Kramos, Balazs³  Izrael, Richard⁴  Olah, Julianna⁴  Nemeth, Tamas¹  Balogh, Gyorgy T.²  Huszthy, Peter¹ 

[1] Budapest Univ Technol & Econ, Dept Organ Chem & Technol, POB 91, H-1521 Budapest, Hungary

[2] Chem Works Gedeon Richter Plc, Compound Profiling Lab, POB 27, H-1475 Budapest, Hungary

[3] Chem Works Gedeon Richter Plc, Spectroscop, POB 27, H-1475 Budapest, Hungary

[4] Budapest Univ Technol & Econ, Dept Inorgan & Analyt Chem, Szent Gellert Ter 4, H-1111 Budapest, Hungary

关键词: Proton-ionizable crown ethers;    Diarylphosphinic acids;    pK(a) determination;    DFT, MD simulations;    Acidity;   

DOI  :  10.1016/j.tet.2016.11.041

来源: Elsevier

【 摘 要 】

Synthesis of acidic new crown ethers containing a diarylphosphinic acid unit has been accomplished. The aromatic rings of the crown ethers were substituted with tert-butyl and nitro groups. Nitro substitution of the crown ethers was investigated. pK(a) determination of the new proton-ionizable crown ethers has been performed, showing the effect of the substituents of the aromatic rings on the acidity. An anomaly was discovered in the pK(a) values and an explanation was given based on quantum mechanical calculations and molecular dynamics simulations. (C) 2016 Elsevier Ltd. All rights reserved.

【 授权许可】

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