• Title/Summary/Keyword: Rate of Substitution

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Nucleophilic Substitution Reactions of Benzoic Anhyrides with Aniline in Methanol-Acetonitrile Mixtures (메탄올-아세토니트릴 혼합용매에서 벤조산 무수물과 아닐린의 친핵성 치환반응)

  • Lee, Byung Choon;Shin, Young Kook;Lee, Seung Woo;Lee, Ik Choon;Lee, Won Heui
    • Journal of the Korean Chemical Society
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    • v.41 no.2
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    • pp.69-76
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    • 1997
  • Kinetic studies for the nucleophilic substitution reactions of the benzoic anhydrides with anilines in methanol-acetonitrile mixtures at$35.0{\circ}C$have been carried out in order to elucidate the reaction mechanism. Individual rate constants$k_{XY}$and$k_{XZ}$were decided from the ratios of the reaction products for the competitive substitution reaction at either one of the two carbonyl carbons in benzoic anhydride. Transition state structure and reaction mechanism were elucidated by the Hammett$p_x,\;p_y$and$p_z$values and cross interaction constant$p_x\;p_y$and$p_zvalues. The reaction of the benzoic anhydride has been proposed to proceed by a frontside attack$S_N2 $mechanism with four-membered ring transition state from unusually large magnitude of the$ρ_X,\;ρ_{XY},\;ρ_{XZ}$and positive$p_Y$values.

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A Study on IFGP Model for Solving Multiobjective Quality Management under Fuzzy Condition

  • Cheong, Jong Shik;Pak, Pyong Ki
    • Journal of Korean Society for Quality Management
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    • v.21 no.2
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    • pp.194-214
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    • 1993
  • This paper purports to study on interactive fuzzy goal programming model which leads to the compromise solution which the decision maker satisfies through the interactive approach. We also attempted to calculate local proxy preference function from utility function of sum-of-logarithms in connection with marginal rate of substitution and interactive approach for the purpose of applying weight of multiobjective function. In an attempt to grasp compromise solution from fuzzy efficient solution, we decided to take the interactive method and presented stopping rule for this.

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MitGEN: Single Nucleotide Polymorphism DB Browser for Human Mitochondrial Genome

  • Park, Hyun Seok;Lee, Seung Uk
    • Genomics & Informatics
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    • v.2 no.3
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    • pp.147-148
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    • 2004
  • Recently completed mitochondrial genome databses from public resources provide us with a better understanding of individual mitochondrial genomes for population genomics. By determining the substitution rate of the genomic sequences, it is plausible to derive dates on the phylogenetic tree and build a chronology of events in the evolution of human species. MitGEN is specially designed as a mitochondrial genome browser for analyzing, comparing and visualizing single nucleotide polymorphism for human mitochondrial genomes between human races for comparative genomics. It is a standalone application and is available free for non-commercial work.

Kinetics and Mechanism of the Anilinolysis of Aryl N,N-Dimethyl Phosphoroamidochloridates in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.753-757
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    • 2014
  • The nucleophilic substitution reactions of Y-aryl N,N-dimethyl phosphoroamidochloridates with substituted anilines and deuterated anilines are kinetically investigated in acetonitrile at $65.0^{\circ}C$. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed based on the positive ${\rho}_{XY}$ value. The deuterium kinetic isotope effects involving deuterated anilines show secondary inverse with all the nucleophiles, rationalized by a dominant backside nucleophilic attack.

Event-Driven Real-Time Simulation Based On The RM Scheduling and Lock-free Shared Objects

  • Park, Hyun Kyoo
    • Journal of the military operations research society of Korea
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    • v.25 no.1
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    • pp.199-214
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    • 1999
  • The Constructive Battle Simulation Model is very important to the recent military training for the substitution of the field training. However, real battlefield systems operate under real-time conditions, they are inherently distributed, concurrent and dynamic. In order to reflect these properties by the computer-based simulation systems which represent real world processes, we have been developing constructive simulation model for several years. Conventionally, scheduling and resource allocation activities which have timing constraints, we elaborated on these issues and developed the simulation system on commercially available hardware and operating system with lock-free resource allocation scheme and rate monotonic scheduling.

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Nucleophilic Substitution Reactions of Thiophenyl Phenylacetate with Benzylamines in Acetonitrile

  • 오혁근;김선경;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.20 no.9
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    • pp.1017-1020
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    • 1999
  • The aminolysis reactions of thiophenyl phenylacetates with benzylamines are investigated in acetonitrile at 55.0℃. Relatively large selectivity parameters, βx≒ 1.5, βz = -1.5~-1.8 and βxz = 0.92 together with the valid reactivity-selectivity principle are consistent with stepwise acyl transfer mechanism with rate limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T ± . The first order kinetics with respect to the benzylamine concentration and the realtively large secondary kinetic isotope effect (kH / kD = 1.2-1.7) involving deuterated benzylamine nucleophiles suggest a four center type transition state in which concurrent leaving group departure and proton transfer are involved.

Physicochemical Properties of Modified Rice Powder for Rice-Based Infant Foods III -Acetylated-coss linkage treatment on rice powder (반고형 이유식의 개발을 위한 변형 쌀가루 제조 및 이화학적 특성 III - 초산-처리 쌀가루)

  • Choi, Jung-Sun;Sohn, Kyung-Hee;Choi, Hee-Sun
    • Journal of the Korean Society of Food Culture
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    • v.12 no.5
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    • pp.469-475
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    • 1997
  • The modification of rice powder was attempted by treatment of acetic acid and epichlorohydrin to improve the functional properties of baby food. The initial gelatinization temperature of rice powder determined by amylograph was decreased from $79.5^{\circ}C$ to $63^{\circ}C$ by modification. The apparent and maxium viscosity of rice paste at $95^{\circ}C$ before and after modification were increased from 92B.U. to 236B.U. and from 100B.U. to 202B.U., respectively. The light transmittance of modified rice paste was increased from the temperature of $60^{\circ}C$ and by increasing the degree of substitution at the fixed temperature, while decrease more or less by the treatment of epichlorohydrin. The degree of retrogradation of the paste was decreased from 28.7 to 18.0 upon modification. The rate of syneresis of modified rice powder was decreased with increasing the drgree of substitution and ,the extend of epichlorohydrin treatment. Syneresis was not observed when acetylated rice powder whose DS value is 0.048 was treated with 0.25% of epichlorohydrin for the formation of cross-linkage. The addition of modified rice powder in preparation of semi-solid type infant food could improve the quality without lowering overall digestibility.

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Experimental Investigation of Electrochemical Corrosion and Chloride Penetration of Concrete Incorporating Colloidal Nanosilica and Silica Fume

  • Garg, Rishav;Garg, Rajni;Singla, Sandeep
    • Journal of Electrochemical Science and Technology
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    • v.12 no.4
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    • pp.440-452
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    • 2021
  • Enhancement of durability and reduction of maintenance cost of concrete, with the implementation of various approaches, has always been a matter of concern to researchers. The integration of pozzolans as a substitute for cement into the concrete is one of the most desirable technique. Silica fume (SF) and colloidal nanosilica (CS) have received a great deal of interest from researchers with their significant performance in improving the durability of concrete. The synergistic role of the micro and nano-silica particles in improving the main characteristics of cemented materials needs to be investigated. This work aims to examine the utility of partial substitution of cement by SF and CS in binary and ternary blends in the improvement of the durability characteristics linked to resistance for electrochemical corrosion using electrical resistivity and half-cell potential analysis and chloride penetration trough rapid chloride penetration test. Furthermore, the effects of this silica mixture on the compressive strength of concrete under normal and aggressive environment have also been investigated. Based on the maximum compression strength of the concrete, the optimal cement substituent ratios have been obtained as 12% SF and 1.5% CS for binary blends. The optimal CS and SF combination mixing ratios has been obtained as 1.0% and 12% respectively for ternary blends. The ternary blends with substitution of cement by optimal percentage of CS and SF exhibited decreased rate for electrochemical corrosion. The strength and durability studies were found in consistence with the microstructural analysis signifying the beneficiary role of CS and SF in upgrading the performance of concrete.

A Study on the Formation of Octanenitrile as a Precursor for Synthesis of Carboxylic Acid (카르복실산 합성전구체(合成前驅體)로서의 옥탄니트릴의 생성반응(生成反應)에 관(關한) 연구(硏究))

  • Kim, Yong-In;Oh, Yang-Hwan;Kim, Kwang-Sik;Lee, Dong-Woo
    • Journal of the Korean Applied Science and Technology
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    • v.6 no.2
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    • pp.29-37
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    • 1989
  • Using the quarternary ammonium salts as phase transfer catalyst, the nucleophilic substitution reaction of 1-chlorooctane with sodium-cyanide was investigate kinetically with respect to the formation of octanenitrile. The product was analyzed with gas chromatograph, and quantity of octanenitrile was measured. The reaction condition was considered by the effect of the reaction temperature, of the species and the amount of catalyst, of the speed of strirring, and of the concentration of reactants. The reaction was carried out in the first order on the concentration of 1-chlorooctane and sodium cyanide, respectively. The over-all order was 2nd. The activation energies for the nucleophilic substitution reaction of 1-chlorooctane and 1-bromooctane under tetrabutylammonium hydrogen-sulfate were calculated as 2.05 and 10.08kcal/mol, respectively. The effect of various caltalysts was decreased in the order of tetrabutylammonium bromide, terabutylammonium, tetrabutylammonium hydrogensulfate, and tetrabutylammonium iodide. The reaction rate was dependent on the concentration of sodium-cyanide dissolved in the aqueous phase, and the good result was shown when the mol ratio between 1-chlorooctane and sodium cyanide was one per three.

Nucleotide Analysis of 185 rRNA and Molecular Phylogeny of the Korean Decapods (하국산 십각류의 18S 리보솜 RNA의 염기분석과 분자계통에 관한 연구)

  • Kim, Won
    • The Korean Journal of Zoology
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    • v.35 no.1
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    • pp.80-86
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    • 1992
  • The nucleotide sequences of 185 rRNAs of the five Korean decapods were partially determined by the direct sequencing method using the reverse transcriptase. ne average GC content of five species was 51.1% which is higher than that of yeast(45.0%) and lower than those of frog (53.0%) and rat (55.6%). This result follows the general patterns of the GC content in the nucleotides of the nucleic acid shown among the various phylogenetic groups. The average ratio of transrional/transversional nucleotide substitution of pairwise comparison among six species (including Anemia salina) was 1.200 $\pm$ 0.310 when whole region alas examined. However, the ratio showed some differences when the conservative regions and variable regions frere separatelv examined. The molecular phylogenies of the five species were constructed by using two different tree making methods. In general the results support the previously reported molecular phylogeny of the decapod crustaceans. However, our results indicate thats in the analysis of the sequence dat3, the UPGMA clustering method of the distance matrix method should be carefully employed after considering the rate of nucneotide substitution in the different regions of the molecule.

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