Neighboring group participation in solvolysis. X. Dissection of Ar1-5 and Ar2-6 pathways in trifluoroacetolysis of 4-arylbutyl 6-methyl-2-naphthalenesulfonates.
スポンサーリンク
概要
- 論文の詳細を見る
Trifluoroacetolysis rates and products were determined for eleven 4-(<I>m</I>- and <I>p</I>-substituted phenyl) butyl 6-methyl-2-naphthalenesulfonates. Most substrates solvolyze predominantly or even exclusively with aryl assisted (<I>k</I><SUB>Δ</SUB>) pathway. Dissection of <I>k</I><SUB>Δ</SUB> into Ar<SUB>1</SUB>-5 and Ar<SUB>2</SUB>-6 components was performed by means of quantitative <SUP>13</SUP>C NMR study of suitably labeled <I>p</I>-methyl and <I>p</I>-fluoro derivatives; the results were 32.4% Ar<SUB>1</SUB>-5 and 67.6% Ar<SUB>2</SUB>-6 for the former and 43.3% Ar<SUB>1</SUB>-5 and 56.7% Ar<SUB>2</SUB>-6 for the latter. For other substrates the dissection was carried out by postulating two independent linear free energy relationships (LFER) for the two pathways determined by the above four partial rates. Ar<SUB>2</SUB>-6 is much prefered over Ar<SUB>1</SUB>-5 through the series; for the unsubstituted derivative 90.6% Ar<SUB>2</SUB>-6 <I>vs</I>. 9.4% Ar<SUB>1</SUB>-5 was determined. A completely different approach by means of non-linear regression analysis of <I>k</I><SUB>Δ</SUB> as a sum of two independent LFER gave fairly different and rather unsettled results, limitations of such an approach being suggested. The characteristics of remote aryl participation are discussed based on the above data.
- 公益社団法人 日本化学会の論文
著者
-
Takai Yoshio
The Institute Of Scientific And Industrial Research Osaka University
-
Yamataka Hiroshi
The Institute Of Scientific And Industrial Research Osaka University
-
Ando Takashi
The Institute of Scientific and Industrial Research, Osaka University
-
Yamawaki Junko
The Institute of Scientific and Industrial Research, Osaka University
-
Saito Yoshimasa
The Institute of Scientific and Industrial Research, Osaka University
関連論文
- Evaluation of Chiral Amino Acid Discrimination by a Permethylated Cyclic Tetrasaccharide, cyclo-{→6)-α-D-Glcp-(1→3)-α-D-Glcp-(1→6)-α-D-Glcp-(1→3)-α-D-Glcp-(1→}, Using FAB Mass Spectrometry
- Estimation of Thermodynamic Parameters on Enantioselective Complexation Equilibria by Temperature-dependent FAB Mass Spectrometry
- Substituent Effect on the Gas Phase Basicity of Pyridine N-Oxide
- Acceleration of the Fluorination of Benzyl Halide by the Combinatoin of Lead Fluoride and Sodium Salt
- A Ketyl Radical Probe Experiment. The Reactions of ο-Halobenzophenones with Various Wittig Reagents
- Neighboring group participation in solvolysis. VII. Trifluoroacetolysis of .OMEGA.-phenylakyl 6-methyl-2-naphthalenesulfonates.
- Neighboring group participation in solvolysis. X. Dissection of Ar1-5 and Ar2-6 pathways in trifluoroacetolysis of 4-arylbutyl 6-methyl-2-naphthalenesulfonates.
- Fluoride salts on alumina as reagents for alkylation of phenols and alcohols.
- Potassium fluoride on alumina. An efficient solid base for elimination, addition, and condensation.
- The Beckmann rearrangement in concentrated sulfuric acid. Studies by means of NMR and kinetic isotope effect.
- Neighboring group participation in solvolysis. XIII. Kinetic isotope effects in solvolysis of 2-arylethyl p-nitrobenzenesulfonates.
- Structural Studies of a Liquid Crystalline Compound, 2-(4-Cyanophenyl)-5-(4-butylphenyl)-1,3,2-dioxaborinane, by Means of Nuclear Magnetic Resonance and X-Ray Analyses.
- MINDO/3 calculations of kinetic isotope effects in heterolysis of neopentyl alcohol.
- Carbon-14 Isotope Effect on sp2sp3 Hybridization in the Prototropic Equilibrium of N-Benzylidenebenzylamine