The Solvent Effect on the Reaction Selectivity in the Chlorination of Propionic Acid

スポンサーリンク

概要

• 論文の詳細を見る

• The chlorinations of propionic acid with chlorine were carried out at 70°C in various solvent mixtures with photo-irradiation or with initiation by benzoyl peroxide. Benzene - CCl<SUB>4</SUB>, naphthalene - CCl<SUB>4</SUB>, and anthracene -CCl<SUB>4</SUB> mixtures, and sulfur dioxide - CCl<SUB>4</SUB> were used as the solvents. In the benzene - CCl<SUB>4</SUB> mixtures, the relative reactivity, β/α, of the a and the α positions of propionic acid changed from 1.68 (CCl<SUB>4</SUB>) to 1.11 (benzene), the ratio being inversely proportional to the electron-donor properties of the solvents. In the naphthalene -CCl<SUB>4</SUB> mixtures, the plot of the relative reactivity, β/α, <I>versus</I> the naphthalene content showed a minimun at <I>ca.</I> 0.1 mol/<I>l</I> of naphthalene; however, the total yield of the chlorinated acids decreased as the content of the naphthalene increased. No chlorinated acids were obtained in the anthracene - CCl<SUB>4</SUB> system. In the presence of sulfur dioxide, the α-position was more readily substituted than the β-position, the β/α ratio decreasing as the molar ratios of C1<SUB>2</SUB>/SO<SUB>2</SUB> were decreased, from 1.3 (Cl<SUB>2</SUB>/SO<SUB>2</SUB>=0.286/0.036) to 0.49 (0.286/0.858), by the initiation of benzoyl peroxide. However, dilution with CCl<SUB>4</SUB> or photo-irradiated chlorination cause no change in the selectivity in spite of the presence of sulfur dioxide. A mechanism to account for such a selectivity has been suggested.

• 公益社団法人 日本化学会の論文

著者

• Tokura Niichiro

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Ryang Hon

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Horikawa Yukio

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Nagai Toshikazu

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

関連論文

• A Common P2 Promoter Polymorphism of the Hepatocyte Nuclear Factor-4α Gene Is Associated with Insulin Secretion in Non-Obese Japanese with Type 2 Diabetes
• PGC-1α Gly482Ser Polymorphism Is Associated with the Plasma Adiponectin Level in Type 2 Diabetic Men
• Association of TCF7L2 polymorphisms with susceptibility to type 2 diabetes in 4,087 Japanese subjects
• Lack of Association of LRP5 and LRP6 Polymorphisms with Type 2 Diabetes Mellitus in the Japanese Population
• Identification of Minimal Promoter and Genetic Variants of Kruppel-like Factor 11 Gene and Association Analysis with Type 2 Diabetes in Japanese
• Calpain-10 (NIDDM1) as a Susceptibility Gene for Common Type 2 Diabetes
• Clinical features of Japanese type 2 diabetics with insulinogenic index in normal range after treatment of glucotoxicity
• Normalization of fasting hyperglycemia is beneficial for successful introduction of small amount of the GLP-1 analog liraglutide in an obese patient with type 2 diabetes mellitus
• The Evaluation of Risk Factors Associated with Adverse Drug Reactions by Metformin in Type 2 Diabetes Mellitus
• Effectiveness of the glucagon test in estimating islet function for liraglutide treatment in a lean diabetic patient with impaired insulin response to glucose
• Reaction Rates in Binary Mixed Solvents. VI. An Sn Ar Reaction in a Methanol-Acetonitrile Mixture
• The E1 Reaction of Menthyl and Neomenthyl Tosylates in Aprotic Solvents
• Solvation of anions in solvent mixtures as deduced from the rates of the Finkelstein reaction.
• The reaction of 4-thiazoline-2-thione with methyl iodide. Solvent effects and pressure effects.
• Solvent Effects under High Pressures. IV. A Procedure for the Estimation of Solvation in the Transition State
• The Reaction of α,α-Dichlorobenzyl Methyl Sulfone with Phenyllithium
• The Carbonylation of Alkyl Halide with Carbon Monoxide in the SbCl5-Liquid Sulfur Dioxide System
• Selective Formations of Several Carboxylic Acids by Carbonylation in the SbCl5–Liquid Sulfur Dioxide System
• The Photochemical Reactions of Tetrahydrofuran and Tetrahydrothiophene with Sulfur Dioxide
• Deoxygenation of Sulfoxides to Sulfides in an Iodine–Pyridine–Sulfur Dioxide System
• The Transformation of the Triphenylmethyl Radical into the Triphenylmethyl Cation in the Sulfur Dioxide - Oxygen System
• Copolymerization of Styrene and Liquid Sulfur Dioxide in the Presence of α-Toluenethiol, 1-Butanethiol, or Bromotrichloromethane
• Hammett Correlation in Mass Spectra. Substituent Effects for the Migratory Aptitude of the Aryl Group in the Unimolecular Ion Decomposition of Diaryl Sulfones
• The Solvent Effect on the Reaction Selectivity in the Chlorination of Propionic Acid
• Isomerization of Gomberg's Trityl by Protonic Acids in Benzene

もっと見る 閉じる

スポンサーリンク