Solvent nucleophilicities of hexafluoroisopropanol/water mixtures

被引:39
作者
Ammer, Johannes [1 ]
Mayr, Herbert [1 ]
机构
[1] Univ Munich, Dept Chem, D-81377 Munich, Germany
关键词
PHOTOLYTIC GENERATION; FLUORINATED ALCOHOLS; CARBOCATIONS; GEPASI;
D O I
10.1002/poc.3064
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
First-order rate constants k1 for the trapping of various donor- and acceptor-substituted benzhydrylium ions in mixtures of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and water ranging from 50 to 99% HFIP (w/w) were determined by laser flash photolytic generation of benzhydrylium ions from benzhydryl triarylphosphonium salts in these solvents. From these rate constants, we derived the solvent-specific reactivity parameters N1 and sN for HFIP/water mixtures as defined by the linear free energy relationship lg k1(20 degrees C)?=?sN(N1?+?E). Copyright (C) 2012 John Wiley & Sons, Ltd.
引用
收藏
页码:59 / 63
页数:5
相关论文
共 35 条
[1]  
ALLARD B, 1983, NOUV J CHIM, V7, P569
[2]   Free Energy Relationships for Reactions of Substituted Benzhydryliunn Ions: From Enthalpy over Entropy to Diffusion Control [J].
Ammer, Johannes ;
Nolte, Christoph ;
Mayr, Herbert .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (33) :13902-13911
[3]   Photolytic Generation of Benzhydryl Cations and Radicals from Quaternary Phosphonium Salts: How Highly Reactive Carbocations Survive Their First Nanoseconds [J].
Ammer, Johannes ;
Sailer, Christian F. ;
Riedle, Eberhard ;
Mayr, Herbert .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (28) :11481-11494
[4]   Fluorinated alcohols:: A new medium for selective and clean reaction [J].
Bégué, JP ;
Bonnet-Delpon, D ;
Crousse, B .
SYNLETT, 2004, (01) :18-29
[5]  
Bentley T.W., 1990, Prog. Phys. Org. Chem, V17, P121, DOI DOI 10.1002/9780470171967.CH5
[6]   EVIDENCE AGAINST APPRECIABLE INTERNAL ION-PAIR RETURN IN THE SOLVOLYSES OF TERTIARY ALIPHATIC HALIDES - MEASUREMENT OF ALPHA-METHYL-HYDROGEN RATE RATIOS IN HEXAFLUOROPROPAN-2-OL-WATER [J].
BENTLEY, TW ;
BOWEN, CT ;
PARKER, W ;
WATT, CIF .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1980, (08) :1244-1252
[7]  
Berkessel A., 2010, MODERN OXIDATION MET, P117
[8]   Dramatic acceleration of olefin epoxidation in fluorinated alcohols: Activation of hydrogen peroxide by multiple H-bond networks [J].
Berkessel, Albrecht ;
Adrio, Jens A. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (41) :13412-13420
[9]  
Chatterjee C, 2007, ACS SYM SER, V949, P379
[10]   Structure of hexafluoroisopropanol-water mixture studied by FTIR-ATR spectra and selected chemometric methods [J].
Czarnik-Matusewicz, Boguslawa ;
Pilorz, Sylwla ;
Zhang, Li-Ping ;
Wu, Yuqing .
JOURNAL OF MOLECULAR STRUCTURE, 2008, 883 :195-202