Acyl cyanide. III. Thermal and base-catalyzed reactions of phenylcarbamoyl cyanide.
スポンサーリンク
概要
- 論文の詳細を見る
Phenylcarbamoyl cyanide (<B>1</B>), under thermal conditions or base-catalysis, behaves as a source of bothphenyl isocyanate and hydrogen cyanide in the syntheses of carbamates, cyanohydrins, and iminohydantoins. The reaction mechanism of <B>1</B> with methanol in the presence of tertiary amine was investigated. The following observations (i–iii) led us to deduce that phenyl isocyanate was not involved as the intermediate and that the rate-determining step involves nucleophilic displacement of <B>1</B> by the alkoxyl group, reinforced by the base: (i) the N–H exchange was too fast to be rate-determining; (ii) <I>d</I>-labelling experiments showed <I>k</I><SUB>H</SUB>/<I>k</I><SUB>D</SUB>=1.8–1.9 in any of the reactions, <B>1</B>-<I>d</I><SUB>1</SUB>+MeOH, <B>1</B>-<I>d</I><SUB>0</SUB>+MeOD, and <B>1</B>-<I>d</I><SUB>1</SUB>+MeOD, and (iii) diphenylcarbamoyl cyanide reacted only 7.2 times slower than did <B>1</B>.
- 公益社団法人 日本化学会の論文
著者
-
Oku Akira
Department Of Chemistry And Materials Technology Kyoto Institute Of Technology
-
Suzuki Takamasa
Department Of Applied Science Faculty Of Engineering Kyushu University
-
Mashio Fujio
Department of Chemistry, Kyoto Institute of Technology
-
Koura Hajime
Department of Chemistry, Kyoto Institute of Technology
関連論文
- Empirical Analysis on the Railroad Development Impact on Local Population Density in Japan
- Asymmetric Synthesis of Functionalized Secondary Alcohols by Catalytic Ring-Cleavage Reactions of Cyclic Acetals Derived from (R)-1, 3-Butanediol
- Donor-Acceptor Binary Photocatalysis System Illustrated by the Intramolecular Cyclization of a Cyclopropanone Acetal Tethered to Cyclohexen-2-one
- Comparative Study of C-V and Transconductance of a Si δ-Doped GaAs FET Structure
- Picosecond Photoluminescence Study of Relaxation Phenomena of Hot Electrons in a Quasi-One-Dimensional Structure
- On the Electron Mobility in Quasi-One-Dimensional Structures Fabricated by Holographic Lithography and Wet Chemical Etching
- Deprotection of Acetals and Silyl Ethers by DDQ. Is DDQ a Neutral Catalyst?
- Development of R4 Gateway Binary Vectors (R4pGWB) Enabling High-Throughput Promoter Swapping for Plant Research
- Improved Gateway Binary Vectors : High-Performance Vectors for Creation of Fusion Constructs in Transgenic Analysis of Plants
- Cyclopropylidene Dianion Equivalent. Preparation of 1,1-Dilithio-2,2-diphenylcyclopropane
- Low-Temperature Magnetic and Structural Transitions of the Quasi-One-Dimensional Magnets TMMC and DMMC at High Pressures : II. LOW TEMPERATURE PROPERTIES OF SOLIDS : Magnetism : Cluster, Low Dimension
- Expression Analysis of Arabidopsis thaliana Small Secreted Protein Genes
- Expression Analysis of Arabidopsis thaliana Small Secreted Protein Genes
- Design of a Novel Cyclopropane Donor Bis (trimethylsilylmethyl) cyclopropane and Its Electron Transfer Reactions
- Enhancement of Electron Mobility in Quasi-One-Dimensional Structure
- POPULATION DENSITY - AUTOMOBILE USE RELATIONSHIP: RE-EXAMINATION IN ASIAN AND AMERICAN MEGA-CITIES:RE-EXAMINATION IN ASIAN AND AMERICAN MEGA-CITIES
- The Peracid-oxidation of Tetraphenylallene: The Formation of Hydroxyindanone and Its Oxidative Transformation
- Acyl cyanide. III. Thermal and base-catalyzed reactions of phenylcarbamoyl cyanide.
- Substituent effects in the Diels-Alder reaction of substituted benzynes with hexamethylcyclohexa-2,4-dienone.
- Acyl cyanide. VI. The synthesis of 1-cyano-1-alkenyl esters by the reaction of acyl cyanides with acid chlorides. Synthesis and mechanism.
- Regio- and stereoselectivity of the intramolecular C-H insertion by cyclopropylidenes bearing a remote oxido substituent.
- A formylcarbonium ion synthon. Synthesis of 3-thio-substituted 2-amino acids and thio-substituted enamines from 2-acyloxyacrylonitriles.
- The synthesis of 1,2,3,4-tetramethyl-5-nitronaphthalene and 1,2,3,4-tetramethyl-6-nitronaphthalene.
- Acyl cyanide. IV. The reduction of phenyl-substituted carbamoyl cyanides with metal hydrides.
- Acyl cyanide. V. The synthesis of 1-cyano-1-alkenyl esters by the reaction of acyl cyanides with acid anhydrides and isocyanates.
- Intramolecular [2+2] photocycloaddition. 5. Synthetic methods toward [2.n]-, [3.n]-, and [4.n]naphthalenophane skeletons by using .ALPHA.,.OMEGA.-bis(vinylnaphthyl)alkanes.