Reinvestigation of the mechanism of the reaction of N,N-dimethylaniline N-oxide with acetic anhydride.
スポンサーリンク
概要
- 論文の詳細を見る
The mechanism of the reaction between <I>N</I>,<I>N</I>-dimethylaniline <I>N</I>-oxide <B>1</B> and acetic anhydride to give 2-acetoxy-<I>N</I>,<I>N</I>-dimethylaniline <B>2a</B> has been reinvestigated by means of our more refined <SUP>18</SUP>O-tracer experiments. Other products of the reaction are 4-acetoxy-<I>N</I>,<I>N</I>-dimethylaniline, <I>N</I>,<I>N</I>-dimethylaniline <B>4</B>, <I>N</I>-methylacetanilide, and bis(4-dimethylaminophenyl)methane. The reaction of <B>1</B> with <SUP>18</SUP>O-labeled acetic anhydride is considered to involve the initial formation of carbonyl-<SUP>18</SUP>O-labeled <I>N</I>-acetoxy-<I>N</I>,<I>N</I>-dimethylanilinium ion <B>7a</B> and the subsequent intramolecular rearrangement of <B>7a</B> into <B>2a</B> in which the original <SUP>18</SUP>O-label in <B>7a</B> is unequally partitioned into two oxygen atoms of <B>2a</B> (phenolic oxygen: ethereal oxygen=<I>ca.</I> 4 : 1). The reaction of <B>1</B> with trichloroacetic anhydride gave solely 2-trichloroacetoxy-<I>N</I>,<I>N</I>-dimethylaniline but not any <B>4</B> which should be formed <I>via</I> the free radical mechanism. These observations suggest the occurrence of the two concerted path <I>via</I> polarized six-(major) and four-(minor) membered cyclic transition states and rule out the free radical pair mechanism which was proposed ealier by us.
- 公益社団法人 日本化学会の論文
著者
-
Fujimori Ken
Department Of Anatomy School Of Medicine Faculty Of Pharmaceutical Sciences Tokushima University
-
Oae Shigeru
Deparment of Applied Chemistry Faculty of Engineering Osaka City University
-
Fujimori Ken
Department of Chemistry, The University of Tsukuba
-
Asai Nobuyoshi
Department of Chemistry, The University of Tsukuba
関連論文
- Triplet Sensitized Laser Flash Photolysis of BNN3, Caged Nitric Oxide
- Design and Synthesis of Dioxetane-Based Chemiluminescent Substrates with High Efficiency in Aqueous System(By a grant Research Institute for Integrated Science, Kanagawa University)
- Mechanistic Aspects of Bioluminescence and Chemiluminescence(By a grant Reserch Institute for Integrated Science, Kanagawa University)
- Studies on Heterogeneity of Fluorescence Labeled Chromatin
- Display on Dehydrogenase Distribution in Tissues by the TRIDENT
- CATCH22 syndrome with qastroesophageal reflux
- Reaction Kinetics of Nitroblue tetrazolium (NBT) Reduction
- Comparative studies on fish tooth tissues by microfluorometry and Raman-spectrometry
- UV-spectrophotometry and fluorophotometry on human tooth tissues
- MULTIPLE DISTRIBUTION OF THE FLUORESCENCE IN HUMAN TEETH (Symposium on the Chinical Application of Histochemistry and Cytochemistry)
- NONLYSOSOMAL GRANULES IN PERITONEAL MACROPHAGES : SUBCELLULAR LOCALIZATION OF NEUTRAL α-GLUCOSIDASE (Cytochemistry of Macrophage)
- Microspectrophotometric characterization of stained blood cells
- Histological and Biochemical Studies on Glycogenosis Type II Induced by the Injection of an Acid Aloha-Glucosidase Inhibitor
- CYTOPHOTOMETRIC DETERMINATION OF GLUTAMIC DEHYDROGENASE ACTIVITY IN MOUSE BRAIN BY USING TRIDENSITY-AUTOMICROPHOTOMETER
- Kinetics of Base Catalyzed Chemiluminescence Reaction of Spiro[adamantane -1,3'-(4'-(m-hydroxyphenyl)-4'-methoxy-1',2'-dioxetane)]
- FORMATION OF GLYCOGENOSOMES IN RAT LIVER INDUCED BY INJECTION OF ACARBOSE, AN α-GLUCOSIDASE INHIBITOR
- The Radiation-induced Addition of Hydrogen Sulfide to Propylene
- The Radiation-induced Reaction of Benzyl Mercaptan and p-Tolyl Mercaptan in Various Organic Solvents
- The Formation of Sulfur Compounds in the Radiolysis of a Toluene Solution of Sulfur
- The Reactions of Cyclic Sulfilimines with Cyanide Ion and Phosphine: Evidence for Substitution on Trivalent Sulfur
- Physical properties and various reactions of thionitrites and related substances.
- Catalytic oxidation of mercaptans by iodine-hydrogen iodide system in dimethyl sulfoxide.
- Oxidative S-dealkylation reaction of sulfide catalyzed by Co(II)(bzacen).
- Enzymatic oxidation of alkyl sulfides by cytochrome P-450 and hydroxyl radical.
- Mechanisms of enzymatic S-oxygenation of thioanisole derivatives and O-demethylation of anisole derivatives promoted by both microsomes and a reconstituted system with purified cytochrome P-450.
- A New Rearrangement Reaction of Azoxybenzene with Arenesulfonyl Chloride
- The Reaction of Azoxybenzene with Acetic Anhydride
- Nucleophilic substitution on 4-methylbenzyl thiocyanate with nucleophiles.
- Mechanism of the Oxygen Exchange Reaction of n-Butyl Methyl Sulfoxide in Sulfuric Acid
- The Reaction of 3H-1,2-Benzodithiole-3-thione with Diphenyldiazomethane
- Kinetic Study of the Pyrolysis of 1- and 2-Phenylethyl Phenyl N-Tosylsulfilimines
- Sulfilimine. XVII. Syntheses and Reactions of N-Carbamoylsulfilimines
- The Reaction of Elemental Sulfur with Organic Compounds. IV. The Reactions of N-Arenesulfonylsulfilimine and Sulfoximine with Sulfur and Diaryl Disulfide
- Elimination and nucleophilic substitution on nitrogen atom. Reactions of -O-aroyl-N,N-di(p-substituted benzyl)- and O-aroyl-N-benzoyl-N-benzylhydroxylamines with various nucleophiles in dipolar aprotic solvents.
- A Novel Reduction of the O-(3,5-Dinitrobenzoyl)-N,N-(aroylary)hydroxylamines by the Cyanide Ion in Dipolar Aprotic Solvents
- Intramolecular stereospecific Pummerer reactions of aryl (substituted-methyl) sulfoxides bearing electron-withdrawing groups with acetic anhydride.
- Deoxygenation of tertiary amine oxides with carbon disulfide.
- Predominant intramolecular Pummerer reactions of substituted benzyl p-tolyl sulfoxides with acetic anhydride.
- Enzymatic oxygenation of sulfides with cytochrome P-450 from rabbit liver. Stereochemistry of sulfoxide formation.
- Unusual reaction of azoxybenzenes with p-toluenesulfonic acid in acetic anhydride.
- Oxygen-18 Scrambling Reaction of Aroyl Alkyl Carbonates
- Reinvestigation of the mechanism of the reaction of N,N-dimethylaniline N-oxide with acetic anhydride.
- Reaction of haloazoxybenzenes with sulfuric acid.
- Reaction of Sulfoxides with Acylating Reagents. IV. The Catalytic Effect of Both the Brönsted and Lewis Acids in the Oxygen Exchange Reaction of Diaryl Sulfoxides with Acetic Anhydride
- Formation and Properties of Phenylthiomethyl Radical. Anodic Oxidation of Sodium Phenylthioacetate and Thermal Decomposition of t-Butyl Phenylthioperacetate
- Reaction of Sulfoxides with Acylating Reagents. III. Mechanism of the Reactions of Phenyl Methyl Sulf oxide with Acetic Anhydride
- A cross-coupling reaction of methylsulfinylarene.
- Intermolecular Pummerer rearrangement reactions of alkyl phenyl and dialkyl sulfoxides with acetic anhydride.
- Tracer Study of the Reactions of Diphenyl Sulfone and Diphenyl Sulfoxide with Diphenyl Disulfide
- The Photochemical Degradation of Diphenyl Sulfone-1-14C
- Synthesis and reaction of 2,2'-biquinolyl.
- Thermal curtius rearrangement of N-acyl-S,S-diphenylsulfilimine.
- Catalytic reduction of sulfoxide by bromine-hydrogen bromide system.
- Nucleophilic Substitution on Trivalent Nitrogen Atom. Menschutkin Type Reaction of O-2,4-Dinitrophenylhydroxylamine with Uncharged Nucleophiles
- Pyrolysis of S-(2-(phenylthio-, phenylsulfinyl-, and phenylsufonyl)-ethyl)-N-p-tosylsulfilimine.