Stereochemical Studies on the Nuclear Alkylation of Phenols with 1-Phenylethyl Chloride and the Acidic Rearrangement of the 1-Phenylethyl Ethers of Phenols in the Phenolic Solvents

スポンサーリンク

概要

• 論文の詳細を見る

• Phenolyses of optically active 1-phenylethyl chloride were carried out in phenol (50°C), <I>p</I>-cresol (100°C), <I>p</I>-chlorophenol (100°C), and 2,6-xylenol (100°C in the presence of variable concentrations of the sodium salts of the respective phenols or triethylamine; the distributions (%) for the O- and C-alkylation products and the net steric courses (α%) for each product were examined. The distribution and the steric course which were graphically extrapolated to the zero base concentration indicated that, if the influence of the liberated hydrogen chloride was excluded, in the phenolyses without an added base the major products are the 1-phenylethyl ethers of the respective phenols with net <I>retained</I> configurations and the minor products are the <I>o</I>-and <I>p</I>-1-phenylethylated phenols with net <I>inverted</I> configurations. The hydrogen chloride rearrangement of the optically active 1-phenylethyl ethers of the respective phenols proceeded rapidly to give <I>o</I>-1-phenylethylated phenols with predominantly <I>retained</I> configurations (for phenol, <I>p</I>-cresol, and <I>p</I>-chlorophenol) and <I>p</I>-1-phenylethylated phenols with net <I>inverted</I> configurations (for phenol and 2,6-xylenol) in the respective phenol–benzene (1:1 by wt) solvents. The <I>p</I>-toluenesulfonic acid rearrangement of 1-phenylethyl phenyl ether-<SUP>18</SUP>O proceeded to give <I>o</I>- and <I>p</I>-1-phenylethylphenols with partial loss of the oxygen-18 atom in the phenol–benzene (1:1 by wt) solvent, indicating the coexistence of the <I>intermolecular</I> course for the acidic rearrangement in the phenolic solvents. From these findings, it is concluded that the formation of the <I>ortho</I>-alkylates with retention of configuration, experimentally observed in the respective phenolyses without an added base, is attributed not to the direct retentive alkylation of the phenols, but to the rapid rearrangement of the 1-phenylethyl ethers with net retention of configuration, caused by the hydrogen chloride liberated in the <I>S</I><SUB>N</SUB>1-phenolysis of 1-phenylethyl chloride in the respective phenolic solvents.

• 公益社団法人 日本化学会の論文

著者

• Makino Osamu

  Department Of Genetics Life Science Institute Sophia University

• KINOSHITA Tomomi

  Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University

• Okamoto Kunio

  Department of Fuel Chemistry Faculty of Engineering Kyoto University

関連論文

• Hydrocarbon Anions with High Stability. Part 2. Structure and Stability of Cyclopentadienide Ions with Condensed Aromatic Rings
• Solvent Effects and Steric Course in the Solvolysis of 1,3,3-Trimethy1-2-oxocyclopentyl Mesylate in Comparison with 1,1,3,3-Tetramethy1-2-oxobutyl System
• Leukoencephalopathy Induced by Low-dose Methotrexate in a Patient with Rheumatoid Arthritis
• High-dose dexamethasone plus antihistamine prevents colorectal cancer patients treated with modified FOLFOX6 from hypersensitivity reactions induced by oxaliplatin
• Isolation of a series of single missense mutants of a dna gene of phage φ29, gene 1, utilizing their inhibitory effect on E. coli growth
• A Variant Protein from φ29 Replication Gene, Gene 1, Did Not Form Homo-Polymer Due to a Single Amino Acid Substitution Near the Carboxyl Terminus
• Kinetic Studies of Solvolysis. IX. The SNl-type Cleavage of t-Butyl p-Substituted-phenyl Ethers and Optically-active α-Phenethyl Phenyl Ether by Hydrogen Halides in a Phenol-Dioxane Solvent
• Phenolysis of exo- and endo-2-Norbornyl p-Toluenesulfonates. Rates and Product Distributions
• Syntheses and properties of di-, tri-, and tetracyclopropyltropylium and di- and tri-t-butyltropylium ions.
• Retentive solvolysis. 13 The number and the stability of carbocation intermediate in the SN1 phenolysis. Salt effect on retentive phenolyses of optically active 2,2-dimethyl-1-(p-substituted phenyl)propyl p-nitrobenzoates.
• The One-electron Reduction of Carbonium Ions. VIII. The Reducibility of Hetero-substituted Tropylium Ions as Measured by the Competitive Reduction Method with Zinc Powder
• Solvolysis in carboxamides. II. Solvolytic elimination of 7.BETA.-methylbicyclo[3.3.1]non-3.BETA.-yl tosylate in carboxamides.
• Syntheses and properties of the polymethylenebis-(diphenylcyclopropenium) dications.
• Synthesis and properties of the tristyrylmethyl anion.
• Solvolysis in carboxamides. VI. Kinetic, product, and deuterium tracer studies on the N,N-dimethylacetamide solvolysis of threo-2-(p-methoxyphenyl)-1-methylpropyl brosylate. Nature of the k.DELTA. pathway.
• Retentive solvolysis. 16. Reinvestigation of the retentive phenolysis of 1-phenylethyl chloride. The mechanism and the structure of ion pair intermediate.
• Solvolysis in carboxamides. V. Solvolytic elimination of threo-1-methyl-2-phenylpropyl brosylate in N,N-dimethylacetamide. Kinetic, product, and deuterium tracer studies.
• Solvolysis in carboxamides. VII. Carboxamide solvolysis of threo-2-aryl-1-methylpropyl brosylates. Reactivity-selectivity relationships as a mechanistic probe.
• The synthesis of the (diacetylmethyl)tropylium ion and its transformation to the 3-acetyl-2-methylfurotropylium ion.
• The One-electron Reduction of Carbonium Ions. VI. The Trapping of the Cycloheptatrienyl Radical with 2-Methyl-2-nitrosopropane in the Course of the Zinc Reduction of the Tropylium Ion
• Synthesis and properties of bis(cyclopropylphenyl)cyclopropenones and the tris(p-cyclopropylphenyl)cyclopropenium ion.
• One-Electron Reduction of Carbonium Ions. III. The Effect of Added Anions on the Rate of Reduction of the Tropylium Ion with Cr(II)
• The Retentive Solvolysis. VII. Structural Effect of the Leaving Group on the Steric Course of the SN1 Phenolysis of 1-Phenylethyl Systems
• The Phenolysis of Tetrahydrolinalyl and 2-Octyl Systems. The Rates, Steric Courses, and Product Distributions
• The Dissociation of 7-Triphenylmethyl-1,3,5-cycloheptatriene in m-Xylene
• Stereochemical Studies on the Nuclear Alkylation of Phenols with 1-Phenylethyl Chloride and the Acidic Rearrangement of the 1-Phenylethyl Ethers of Phenols in the Phenolic Solvents
• Solvolysis of cis- and trans-4-t-Butylcyclohexyl Tosylates in N-Methylacetamide. Rates and Products Distribution

もっと見る 閉じる

スポンサーリンク