caa a22 4500 467948127 CHVBK 20180405193739.0 cr unu---uuuuu 170328e20050101xx s 000 0 eng 10.1007/s10975-005-0031-x doi (NATIONALLICENCE)springer-10.1007/s10975-005-0031-x (NATIONALLICENCE)springer-10.1007/PL00021980 Mechanism of the hydrolysis of N-aryliminotriphenylphosphoranes [Elektronische Daten] [S.-Y. Pyun, Y.-H. Lee, T.-R. Kim] Hydrolysis reactions of N-aryliminotriphenylphosphoranes (I) at varying pH have been investigated kinetically. The reactions produced aniline derivatives and triphenylphosphine oxide as the products. The reactions are first-order, and the Hammett ρ values are −0.29 and −0.63 at pH 3.0 and 8.0, respectively. The reaction rate increased linearly with acetate ion concentration at [AcO−] < 0.05 M and approached a limiting value at higher base concentration. The plot of logk t versus pH shows that there are two different regions in the rate profile; one part in which logk t increases with hydronium ion concentration and the other where k t is a constant regardless of pH. On the basis of these results, a plausible hydrolysis mechanism is proposed. At pH < 8.0, the reaction proceeds by protonation of the iminophosphorane nitrogen atom, followed by the addition of a water molecule. At pH > 8.0, the proton transfer from water to α-nitrogen of the iminophosphorane becomes the rate limiting step. MAIK "Nauka/Interperiodica”, 2005 Pyun S.-Y Department of Chemistry, Pukyong National University, Pusan, 608-737, Korea aut Lee Y.-H Department of Chemistry, Wonkwang University, 570-749, Chunbuk, Korea aut Kim T.-R Department of Chemistry, Korea University, 1-Anamdong Seoul, 136-701, Korea aut Kinetics and Catalysis Nauka/Interperiodica 46/1(2005-01-01), 21-28 0023-1584 46:1<21 2005 46 10975 https://doi.org/10.1007/s10975-005-0031-x text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10975-005-0031-x text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Lee Y.-H Department of Chemistry, Wonkwang University, 570-749, Chunbuk, Korea aut NATIONALLICENCE 700 1- Pyun S.-Y Department of Chemistry, Pukyong National University, Pusan, 608-737, Korea aut NATIONALLICENCE 700 1- Kim T.-R Department of Chemistry, Korea University, 1-Anamdong Seoul, 136-701, Korea aut NATIONALLICENCE 773 0- Kinetics and Catalysis Nauka/Interperiodica 46/1(2005-01-01), 21-28 0023-1584 46:1<21 2005 46 10975 NATIONALLICENCE 856 40 https://doi.org/10.1007/PL00021980 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Lee Y.-H Department of Chemistry, Wonkwang University, 0-749, Chunbuk, Korea aut Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE NATIONALLICENCE NL-springer