caa a22 4500 467951470 CHVBK 20180405193742.0 cr unu---uuuuu 170328e20050101xx s 000 0 eng 10.1007/s10975-005-0033-8 doi (NATIONALLICENCE)springer-10.1007/s10975-005-0033-8 (NATIONALLICENCE)springer-10.1007/PL00021981 Solvation bifunctional catalysis of the hydrolysis of sulfonyl chlorides by hydration complexes of 2-propanol: influence of the substrate structure [Elektronische Daten] [S. Ivanov, A. Mikhailov, B. Gnedin, A. Lebedukho, V. Korolev] The temperature dependence of rate constants for the pseudo-first-order hydrolysis of 2-methylbenzenesulfonyl chloride, 1,5-naphthalenedisulfonyl chloride, and 4-acetamidobenzenesulfonyl chloride in water-2-propanol mixtures is studied in the i-PrOH mole fraction range x2 = 0−0.10. The concentration dependences of the enthalpy of activation and the entropy contribution (ϑ = 100(−TΔS≠)/(ΔG≠, %) for the hydrolyses of all sulfonyl chlorides are nonmonotonic, depending on the sulfonyl chloride structure and the degree of complementarity of the hydration complexes to the solvent structure. The sulfonyl chlorides are hydrolyzed via two pathways: one of them involves a water dimer as a bifunctional catalyst along with a water molecule as a nucleophile, and the other involves an alcohol hydrate. MAIK "Nauka/Interperiodica”, 2005 Ivanov S. Ivanovo State University, Ivanovo, Russia aut Mikhailov A. Institute of Chemistry of Solutions, Russian Academy of Sciences, 153045, Ivanovo, Russia aut Gnedin B. Ivanovo State University, Ivanovo, Russia aut Lebedukho A. Ivanovo State University, Ivanovo, Russia aut Korolev V. Institute of Chemistry of Solutions, Russian Academy of Sciences, 153045, Ivanovo, Russia aut Kinetics and Catalysis Nauka/Interperiodica 46/1(2005-01-01), 29-36 0023-1584 46:1<29 2005 46 10975 https://doi.org/10.1007/s10975-005-0033-8 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10975-005-0033-8 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ivanov S. Ivanovo State University, Ivanovo, Russia aut NATIONALLICENCE 700 1- Mikhailov A. Institute of Chemistry of Solutions, Russian Academy of Sciences, 153045, Ivanovo, Russia aut NATIONALLICENCE 700 1- Gnedin B. Ivanovo State University, Ivanovo, Russia aut NATIONALLICENCE 700 1- Lebedukho A. Ivanovo State University, Ivanovo, Russia aut NATIONALLICENCE 700 1- Korolev V. Institute of Chemistry of Solutions, Russian Academy of Sciences, 153045, Ivanovo, Russia aut NATIONALLICENCE 773 0- Kinetics and Catalysis Nauka/Interperiodica 46/1(2005-01-01), 29-36 0023-1584 46:1<29 2005 46 10975 NATIONALLICENCE 856 40 https://doi.org/10.1007/PL00021981 text/html Onlinezugriff via DOI Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE NATIONALLICENCE NL-springer