Pyrolysis of sulforxide bearing electron-withdrawing substituents on .BETA.-position in S-ethyl group of ethyl phenyl sulfoxide.
スポンサーリンク
概要
- 論文の詳細を見る
In order to obtain information concerning the reaction mechanism of the pyrolysis of a sulfoxide bearing an electron-withdrawing substituent on the β-position in the <I>S</I>-ethyl group of ethyl phenyl sulfoxide, 2-(substituted phenyl)ethyl aryl sulfoxides(<B>1</B>) and 2-cyanoethyl (substituted phenyl) sulfoxides(<B>2</B>) were pyrolyzed. The rate-enhancing effect of the β-phenyl group of <B>1</B> was small. The activation enthalpy and entropy of <B>1</B> were found to be 110 kJ mol<SUP>−1</SUP> and −45 JK<SUP>−1</SUP> mol<SUP>−1</SUP>, respectively. Hammett plots for <B>1</B> gave positive trends for the substituents, both on the β-phenyl group (ρ=0.76) and on the <I>S</I>-phenyl group (ρ=0.32), though the ρ-value of the latter was about half of the former. On the other hand, the Hammett plot for <B>2</B> did not give a straight line, but a concave curve in which a series of substituents from the <I>p</I>-OCH<SUB>3</SUB> to <I>p</I>-Cl groups gave a negative trend (ρ=−0.49), while the <I>p</I>-NO<SUB>2</SUB> group afforded a positive trend. The pyrolytic rate of <B>2</B> was found to be about 23-times faster than that of <B>1</B> at 100 °C. The kinetic isotope effect for β-position hydrogen in the β-phenylethyl group of <B>1</B> was considerably large (<I>k</I><SUB>H</SUB>⁄<I>k</I><SUB>D</SUB>=4.3). From the obtained results, it was suggested that the pyrolysis of <B>1</B> and <B>2</B> proceeds via a nearly carbanion-like mechanism in a five-membered cyclic transition state.
- 公益社団法人 日本化学会の論文
著者
-
Yoshizawa Masaki
Department Of Electrical And Electronics Engineering Sophia University
-
Tsukurimichi Eiichi
Department Of Chemical And Biochemical Engineering Faculty Of Engineering Toyama University
-
Yoshimura Toshiaki
Department of Industrial Chemistry, Faculty of Engineering, Toyama University
-
Yoshimura Toshiaki
Department of Applied Chemistry, Faculty of Engineering, Osaka City University
-
Yoshizawa Masaki
Department of Industrial Chemistry, Faculty of Engineering, Toyama University
-
Tsukurimichi Eiichi
Department of Industrial Chemistry, Faculty of Engineering, Toyama University
関連論文
- Separation of Serine Proteases by Polymers Bearing Irreversible Inhibitors
- PEG-Inhibitor Conjugates : Application of Diphenyl α-Aminoalkylphosphonate to Removal of Chymotrypsin(Biochemistry & Molecular Biology)
- Synthesis and Crystal Structures of [CuCl_2(μ-NSPh_3)]_2 and [CuCl_2(Ph_3SN)_2] : Novel Copper Complexes Bearing Organic λ^6-Sulfanenitrile as Ligand
- Selective Removal of Chymotrypsin Using Diphenyl α-Aminoalkylphosphonate Immobilized on Sepharose Gel(Biochemistry & Molecular Biology)
- Design of α-Amylase Inhibitory Peptides
- Kinetic Investigation on the Hydrolysis of Aryl(fluoro)(phenyl)-λ^6-sulfaneitriles
- Cyclic and Linear Peptides Derived from α-Amylase Inhibitory Protein Tendamistat^1
- Growth of Self-Organized GaN Nanostructures on Al_20_3(0001)by RF-Radical Source Molecular Beam Epitaxy
- Study of the Mechanism for the Hydrolysis of Alkoxy(aryl)(phenyl)-λ^6-sulfanenitriles, ArPhS(OR)(〓N)
- α-Amylase Inhibitory Activity of Linear and Cyclic Peptides Derived from Tendamistat
- Selective Removal of Chymotrypsin Using Its Irreversible Inhibitor
- Preparation and Reactivity of N-Substituted S,S,S-Triphenyliminosulfonium Salts
- Synthesis of Fluorescent Peptides and Application for β-Structural Peptide
- Amphiphilic Peptides from pH-Dependent β-Structure in Phospholipid Membrane
- Biological and Structural Properties of Cyclic Peptides Derived from the α-Amylase Inhibitor Tendamistat
- Synthesis, Structure, and Thermolysis Mechanism of S-Alkoxythiazynes
- Synthesis and Reactivity of S-Sulfiliminothiazynes
- Interaction of Synthetic J Protein of Bacteriophage ΦK with Its Circular Single-Stranded DNA
- Synthesis and Properties of Cyclic Peptides Having Inhibitory Site of α-Amylase Inhibitor Tendamistat
- Thermal Decomposition and Mass Spectra of the N-Phenyl-, N, N'-Diphenyl-, and N, N', N''-Triphenylphosphoric Triamides
- Effects of the Noncyclic Cyanamides on the Retrogradation of Waxy Corn Starch
- Simple Determination Method of Degree of Substitution for Starch Acetate
- Comparison of Thermal and Guanidine Hydrochloride Denaturation Behaviors of Glucoamylase from the STA1 Gene of Saccharomyces cerevisiae var. diastaticus
- Preparation and Reactivities of S,S-Diaryl-S-aminothiazynes, Ar_2S(NR_2)(N)^
- First Preparation and Reactions of S, S-Diaryl-S-fluorothiazynes, Ar_2SF(N)
- Studies on the Retrogradation and Structural Properties of Waxy Corn Starch
- Synthesis of Cyclic Peptides Derived from α-Amylase Inhibitor Tendamistat and Their Biological Activity
- Super-Secondary Structure with Amphiphilic β-Standards Probed by Pyrenylalanine
- Model Reaction of Self-Condensation of Sulfenic Acids. Kinetic Investigation for the Reaction of Methyl Benzenesulfenate with trans-Decalin-9-sulfenic Acid^# and 2-Methyl-2-propanesulfenic Acid
- Intramolecular stereospecific Pummerer reactions of aryl (substituted-methyl) sulfoxides bearing electron-withdrawing groups with acetic anhydride.
- Pyrolysis of sulforxide bearing electron-withdrawing substituents on .BETA.-position in S-ethyl group of ethyl phenyl sulfoxide.
- Kinetic study on the alkaline hydrolysis of S,S-diaryl-N-halosulfilimines.
- Thermal decomposition and mass spectra of phosphoramidate esters.
- Mechanism of Reaction of S,S-Diphenyl-S-methoxythiazyne with Thiols.
- Deoxygenation of tertiary amine oxides with carbon disulfide.
- Predominant intramolecular Pummerer reactions of substituted benzyl p-tolyl sulfoxides with acetic anhydride.
- The Ei reaction of substituted threo- and erythro-1-phenylethyl phenyl sulfoxides.
- Intermolecular Pummerer rearrangement reactions of alkyl phenyl and dialkyl sulfoxides with acetic anhydride.