Tri(hetero)substituted Carbonium Ions. II. 2-Dialkylamino-1,3-dithiolanylium Ions. Reactions with Nucleophiles and Ambident Behaviors
スポンサーリンク
概要
- 論文の詳細を見る
The reactions of 2-dialkylamino-1,3-dithiolanylium perchlorates with a variety of nucleophilic species including oxygen, sulfur and nitrogen nucleophiles have been investigated. Examination of the isolated products reveals that these trihetrosubstituted carbonium ions behave as ambident electrophiles toward nucleophiles with two reactive sites, <I>i.e</I>., the electron-deficient centered carbon (a) and the ring-methylene carbon atom (b), and that the nature of nucleophiles greatly affects the reaction course in a straightforward manner. The reaction course may be classified as follows. If the nucleophile is basic, the reaction at the site (a) (mode A) is favored, but if it has large sub-stituents, the initial proton abstraction reaction (mode C) is predominant, while if the nucleophile is polarizable, the reaction at the site (b) (mode B) is favored. The major factor deciding the reaction course is discussed in terms of the schematic energy profile of the overall reaction.
- 公益社団法人 日本化学会の論文
著者
-
OKAWARA Makoto
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
-
Okawara Makoto
Research Laboratory Of Resources Utilization Tokyo Institute Of Technology
-
Nakai Takeshi
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
-
Nakai Takeshi
Research Laboratory of Resouces Utilization, Tokyo Institute of Technology
関連論文
- Acetohydroxamic Acid for Peptide Synthesis
- Polymers Having Stable Radicals : Electrochemical and Chemical Behaviors of the Polymer Having Nitroxyls.
- Enantioselective Peptide Synthesis by Using the Optically Active Polymer Containing the 1-Benzyl-3-Hydroxy-5-Isobutyl-Hydantoin Structure
- Convenient synthesis of .ALPHA.-mercaptoalkanoic acid esters using S-cyanomethyl thiocarbamates.
- Reduction of alloxan by cyanide ion. Isolation of alloxan radical anion salts and alloxantin.
- Tri(hetero)substituted Carbonium Ions. I. Neighboring-Group Participation of the N,N-Dimethyldithiocarbamate Function Involving the Intermediacy of 2-Dimethylamino-1,3-dithiolanylium Ion
- Tri(hetero)substituted Carbonium Ions. II. 2-Dialkylamino-1,3-dithiolanylium Ions. Reactions with Nucleophiles and Ambident Behaviors
- 2-Substituted Imino-1,3-dithiolanes. Their Thermal Ring-isomerizations and Reactions with Epoxides
- Acyl transfer from S-monoacyldihydrolipoamide to benzylamine in the presence of oxidizing agents.
- Tri(hetero)substituted Carbonium Ions. III. Ring-size Effects on the Dual Reactivities of 2-Dimethylamino-1,3-dithiolanylium Ion and Its Ring Analogs as Ambident Electrophiles
- Tri(hetero) substituted Carbonium Ions. VI. An Anomalous Reaction of 2-Methylthio-1,3-dithiolanylium Ion with N,N-Dimethyldithiocarbamate Anion
- Tri(hetero)substituted Carbonium Ions. IV. Reactions of N,N′-Dimethyl-S,S′-dimethyldithiocarbamidium Ion with Various Nucleophiles
- Reactions of Various Thione-compounds with Epoxides. A New Method for the Transformation of the C=S Bond into the C=O
- Reactions of 4-acyl-2-phenyl-1,3,4-oxadiazoline-5-thiones with alcohols in the presence of metal ions.
- Liquid phase peptide synthesis by fragment condensation on soluble polymer support. IV. Relative reactivities of N-t-butoxycarbonyl(Boc)amino acids and Boc-oligopeptide acids in their esterification with soluble chloromethylated polystyrene.
- The Dehydration of N-Benzyloxy and N-Hydroxymaleamic Acid and the Isomerization of N-Benzyloxyisomaleimide
- Imidothiocarbonates. V. Preparations and Properties of Novel Azomethine Ylides and Thiocarbonyl Ylides from Sulfur-contained Heterocycles
- Syntheses and Reactions of Functional Polymers. LVII. Synthesis and Polymerization of Isopropenyl-1,3,4-oxadiazolin-5-ones
- Ring-opening Polymerization of 2-Methyl-1,3,4-oxadiazolin-5-one
- Tri(hetero)substituted Carbonium Ions. VIII. The Hydride Reduction of Cyclic and Open-chain Dithiocarbamidium Salts
- Iminodithiocarbonates. IV. Pyrolyses of N-Acyl Immonium Salts of Iminodithiocarbonates
- Syntheses and Reactions of Functional Polymers. LIV. Syntheses and Polymerizations of O-Substituted-N-hydroxymaleimides
- Iminodithiocarbonates. III. Reactions with Some Electrophiles and the Structural Effect on Nucleophilic Reactivities and Basicities
- Tri(hetero)substituted carbonium ions. XI. A novel synthetic route to 2-dialkylamino-4-alkyl-1,3-dithiolium salts.
- (1,3-Dithiolan-2-yl)trimethylammonium Iodide. An Electrophilic Dithiolanylating Reagent