Kinetic study of the reactions of phenacyl benzoates with trialkyl phosphites.
スポンサーリンク
概要
- 論文の詳細を見る
The reactions of phenacyl benzoates, X–C<SUB>6</SUB>H<SUB>4</SUB>COCH<SUB>2</SUB>OCOC<SUB>6</SUB>H<SUB>4</SUB>–Y (<B>1a</B>–<B>i</B>), with trialkyl phosphites (<B>2a</B>–<B>c</B>) giving dialkyl 1-arylvinyl phosphates (<B>3a</B>–<B>d</B>) in high yields were studied kinetically using the GLC technique. The overall reactions are second order, and exhibit a moderate solvent effect and catalysis upon the addition of certain organic acids. The activation energy, <I>E</I><SUB>a</SUB>=16.5 kcal/mol, and entropy, <I>ΔS</I><SUP>\neweq</SUP>=−38.5 e.u., were obtained from the reaction of <B>1a</B> with <B>2b</B>, and the ρ value obtained using σ for reactions of the two series of <B>1a</B> with <B>2b</B> was ρ<SUB>x</SUB>=3.4 and ρ<SUB>Y</SUB>=1.0, respectively. The reactivity of <B>2</B> in this reaction is markedly increased in the order, Me<Et<<I>i</I>-Pr. These and other data accumulated support a mechanism for this reaction involving a ratedetermining addition of phosphorus atoms in <B>2</B> to the carbonyl carbon of the phenacyl group followed by rearrangement of the phosphorus moiety to the carbonyl oxygen of the phenacyl group.
- 公益社団法人 日本化学会の論文
著者
-
Furukawa Isao
Department Of Molecular Science And Technology Faculty Of Engineering Doshisha University
-
Hashimoto Shizunobu
Department of Applied Chemistry, Faculty of Engineering, Doshisha University
-
Hashimoto Shizunobu
Department of Applied Chemistry, Doshisha University
-
Tatsumi Takao
Department of Applied Chemistry, Faculty of Engineering, Doshisha University
関連論文
- Formal Hydroallylation of Carbon-Carbon Triple Bonds via Tantalum-Alkyne Complexes. Stereoselective Preparation of 1,4-Dienes
- Transition Metal-Catalyzed Cyclization of 2-Allylphenol to 2,3-Dihydro-2-methylbenzofuran without β-Elimination
- α-Amino acidate-Ru(II) Catalysts for Asymmetric Transfer Hydrogenation: First Utilization ofα-Amino Acids as Efficient Ligand
- Synthesis of 3-Ethoxyisoxazole Derivatives and 3-Ethoxy-1H-pyrazole Derivatives from β-Oxo Thionoesters
- Selective Adsorption of Metal Ions on Novel Chitosan-Supported Sulfonic Acid Resin.
- Self aggregation of cationic porphyrin in water.
- A novel synthesis of phenyl carboxylates.
- Exciplexes in perfluorohydrocarbon. Charge-transfer interaction between exciplexes and perfluorohexane.
- Thermal and photochemical reactions of 10-methyl-9-phenylacridinium chloride in alcohols.
- Photochemical Reduction of Nitrobenzene and Its Reduction Intermediates. IX. The Photochemical Reduction of 4-Nitropyridine in a Hydrochloric Acid-Isopropyl Alcohol Solution
- Fluorescence quenching of perfluoronaphthalene by triethylamine.
- Kinetic study of the reactions of phenacyl benzoates with trialkyl phosphites.
- Strong van der Waals interactions in water. Molecular complexes of porphyrins and quinones in organic and aqueous media.