• Title/Summary/Keyword: Leaving group

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Kinetic Studies on Nucleophilic Substitution Reaction of Phenacyl Halides with Pyridines in MeOH-MeCN Mixtures (메탄올-아세토니트릴 혼합용매계에서 할로겐화 펜아실과 피리딘유도체와의 친핵성 치환반응에 대한 속도론적 연구)

  • 구인선;양기열;박종근;이익춘
    • Journal of the Korean Chemical Society
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    • v.41 no.1
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    • pp.22-46
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    • 1997
  • Kinetic studies on nucleophilic substitution reaction of phenacyl bromide and phenacyl chloride with pyridines were conducted at 25℃ and 35℃ in methanol-acetonitrile solvents mixtures. It was shown that the reaction proceeds via an SN2 reaction mechanism based on the transition state parameters, ΔH≠ and ΔS≠ and Bro nsted β values. Quantum mechanical model predicted a product-like transition state, where bond-formation is much more progressed than bond breaking, upon changing the leaving group to that with a better leaving ability.

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Kinetics and Mechanism of the Benzylaminolysis of O,O-Dimethyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4304-4308
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    • 2011
  • Kinetic studies of the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots for substituent X variations in the nucleophiles are discrete with a break region between 4-Me and H, while the Hammett plots (log $k_2$ vs ${\sigma}_Z$) for substituent Z variations in the leaving groups are linear. The sign of the cross-interaction constant (${\rho}_{XZ}$) is positive for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ (= 2.54) value is observed with the weakly basic nucleophiles compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = 0.17). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a stepwise with a rate-limiting leaving group expulsion from the intermediate involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles.

Fabrication of Colloidal Clusters of Polymer Microspheres and Nonspherical Hollow Micro-particles from Pickering Emulsions

  • Cho, Young-Sang;Kim, Tae-Yeol;Yi, Gi-Ra;Kim, Young-Kuk;Choi, Chul-Jin
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.159-166
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    • 2012
  • We have introduced the Pickering emulsion systems to generate novel confining geometries for the selforganization of monodisperse polymer microspheres using nanoparticle-stabilized emulsion droplets encapsulating the building block particles. Then, through the slow evaporation of emulsion phases by heating, these microspheres were packed into regular polyhedral colloidal clusters covered with nanoparticle-stabilizers made of silica. Furthermore, polymer composite colloidal clusters were burnt out leaving nonspherical hollow micro-particles, in which the configurations of the cluster structure were preserved during calcination. The selfassembled porous architectures in this study will be potentially useful in various applications such as novel building block particles or supporting materials for catalysis or gas adsorption.

The Estimation of Patient's Waiting-Time Using Parking Time (주차시간을 이용한 외래환자 대기시간 추정)

  • Song, Jung-Hup
    • Quality Improvement in Health Care
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    • v.2 no.2
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    • pp.20-30
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    • 1996
  • Background : Theoretically as the waiting-time of patient is estimated in queueing, many men and much money are needed. But being the estimation of patient s waiting-time very important in hospital service, so the continuous monitoring of waiting-time is inevitable. To verify that the estimation of waiting-time using parking time is economical, effective and continuous monitoring method and to develop utilizing the method, this study was done. Method : In parking confirmation office, the personnel of parking office wrote parking confirm time, chart number and whether medical examination and treatment finish or not in parking ticket. The next day the parking tickets were gathered and the above data were input. The input parking data were connected with the hospital outpatient file indexing chart number. Then the patient' s data for department, new patient or not, reservation or not, receipt time and payment time were retrieved. The group for finishing medical treatment were compared with that for not finishing in average time lag between confirmation and out-time for hospital. And In-time for hospital, receipt time, payment and out-time for hospital were also analyzed. Result : Confirming parking ticket, the group for finished medical treatment left hospital after 7 minutes. This result showed that the patient for finished medical treatment left hospital immediately. So parking time was reasonable to estimation of hospital-time was concluded. The time for medical treatment, diagnosis and test was constant for all patients and short for waiting time, Then I concluded that the parking time was reasonable for estimation patient's waiting time. Overall patient's waiting time was 113 minutes and new patient's time was 149 minutes, old patient's times was 109 minutes. Waiting time for reservation patient was 98 minutes and for non reservation patient was 122 minutes. The time from hospital arrival to payment was 50 minutes for the group of reservation patient and 69 minutes for non-reservation group. The time from payment to hospital leaving was 51 minutes and 56 minutes for non reservation group. The short time difference between reserved group and not reserved group from payment to hospital leaving time was due to bottle neck effect. Conclusion : The estimation of patient's waiting time using parking time was reasonable because the possession of car was common and the time for medical treatment was equal and the patient after treatment left hospital immediately. Using this method, timely, fast evaluation and continuous monitoring of the intervention effect were possible.

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Exploiting Group Social Capital in Systems Development Projects

  • Park, Jun-Gi;Lee, Seyoon;Lim, Gyoo Gun;Lee, Jungwoo
    • Journal of Information Technology Services
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    • v.15 no.1
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    • pp.131-152
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    • 2016
  • Group social capital can be defined as an intangible asset that promotes knowledge sharing and social interaction. It is posited here that the group social capital raised and nurtured among group members positively influences on team performance in IS (Information Systems) development projects. And communication effectiveness is selected as a critical antecedent and its detailed relationships with the dimensions of group social capital are analyzed. Effective communication plays important role in ISD project teams by integrating knowledge from different areas. Moderating effects of project phase between the sub-dimensions of social capital and project performance are investigated. Hypotheses are tested using data from 131 project teams of 85 manufacturing firms. The results indicated that Communication effectiveness positively impacted sub-dimensions of social capital (social ties, trust, and shared vision). Moreover, the team performance is influenced by shared vision and trust, leaving social ties as a leading subcontract, as theoretically proposed in prior research. The project phase moderates the impact of shared vision on team performance.

Aminolysis of Benzyl 4-Pyridyl Carbonate in Acetonitrile: Effect of Modification of Leaving Group from 2-Pyridyloxide to 4-Pyridyloxide on Reactivity and Reaction Mechanism

  • Bae, Ae-Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2719-2723
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    • 2012
  • A kinetic study is reported for nucleophilic substitution reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in MeCN. The plot of pseudo-first-order rate constant ($k_{obsd}$) vs. [amine] curves upward, which is typical for reactions reported previously to proceed through a stepwise mechanism with two intermediates (i.e., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). Dissection of $k_{obsd}$ into the second- and third-order rate constants (i.e., $Kk_2$ and $Kk_3$, respectively) reveals that $Kk_3$ is significantly larger than $Kk_2$, indicating that the reactions proceed mainly through the deprotonation pathway (i.e., the $k_3$ process) in a high [amine] region. This contrasts to the recent report that the corresponding aminolysis of benzyl 2-pyridyl carbonate 5 proceeds through a forced concerted mechanism. An intramolecular H-bonding interaction was suggested to force the reactions of 5 to proceed through a concerted mechanism, since it could accelerate the rate of leaving-group expulsion (i.e., an increase in $k_2$). However, such H-bonding interaction, which could increase $k_2$, is structurally impossible for the reactions of 6. Thus, presence or absence of an intramolecular H-bonding interaction has been suggested to be responsible for the contrasting reaction mechanisms (i.e., a forced concerted mechanism for the reaction of 5 vs. a stepwise mechanism with $T^{\pm}$ and $T^-$ as intermediates for that of 6).

In Vitro Cytotoxicity of Pt(II) Complexes Containing Ethylenediamine in Rabbit Kidney Proximal Tubular and Human Renal Cortical Cells (에틸렌디아민을 배위자로 한 백금(II)착체의 토끼 및 인체 신장세포에 대한 in vitro 독성)

  • Rho, Young-Soo;Lee, Kyung-Tae;Jung, Jee-Chang;Chang, Sung-Goo
    • YAKHAK HOEJI
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    • v.40 no.2
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    • pp.218-224
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    • 1996
  • This laboratory has recently reported the synthesis and in vitro antitumor activity of PT(II) complexes containing ethylenediamine and diphosphine. In view of the reports of others, cisplatin is toxic to the kidney since the kidney's vulnerability to PT(II) complexes may originate in its ability to accumulate and retain platinum to a greater degree than other organs. The in vitro cytotoxicity of these synthetic PT(II) complexes on the primary cultured proximal tubular cells of rabbit kidney and renal cortical cells of human kidney was investigated. Three endpoints for cytotoxicity tests were evaluated:3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT), $^3H$-thymidine uptake and the glucose consumption tests. The rank order of sensitivity exhibited $^3H$-thymidine uptake>MTT>glucose consumption test. The agents with diphosphine leaving group were significantly less cytotoxic than cisplatin. Moreover, 1,2-bis(diphenylphosphino)ethane (DPPE) exhibited less cytotoxicity than 1.3-bis (diphenylphosphino)propane (DPPP) against on rabbit and human cultured kidney cells. Based on these results, the decreased nephrotoxicity of these new complexes over cisplatin appeared to be partially attributable to a leaving group of DPPP and DPPE. This novel class of platinum compound represents a valuable lead in the development of a "third-generation" agent.

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ATMOSPHERIC CORRECTION TECHNIQUE FOR GEOSTATIONARY OCEAN COLOR IMAGER (GOCI) ON COMS

  • Shanmugam, Palanisamy;Ahn, Yu-Hwan
    • Proceedings of the KSRS Conference
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    • v.1
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    • pp.467-470
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    • 2006
  • Geostationary Ocean Color Imager (GOCI) onboard its Communication Ocean and Meteorological Satellite (COMS) is scheduled for launch in 2008. GOCI includes the eight visible-to-near-infrared (NIR) bands, 0.5km pixel resolution, and a coverage region of 2500 ${\times}$ 2500km centered at 36N and 130E. GOCI has had the scope of its objectives broadened to understand the role of the oceans and ocean productivity in the climate system, biogeochemical variables, geological and biological response to physical dynamics and to detect and monitor toxic algal blooms of notable extension through observations of ocean color. To achieve these mission objectives, it is necessary to develop an atmospheric correction technique which is capable of delivering geophysical products, particularly for highly turbid coastal regions that are often dominated by strongly absorbing aerosols from the adjacent continental/desert areas. In this paper, we present a more realistic and cost-effective atmospheric correction method which takes into account the contribution of NIR radiances and include specialized models for strongly absorbing aerosols. This method was tested extensively on SeaWiFS ocean color imagery acquired over the Northwest Pacific waters. While the standard SeaWiFS atmospheric correction algorithm showed a pronounced overcorrection in the violet/blue or a complete failure in the presence of strongly absorbing aerosols (Asian dust or Yellow dust) over these regions, the new method was able to retrieve the water-leaving radiance and chlorophyll concentrations that were consistent with the in-situ observations. Such comparison demonstrated the efficiency of the new method in terms of removing the effects of highly absorbing aerosols and improving the accuracy of water-leaving radiance and chlorophyll retrievals with SeaWiFS imagery.

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Kinetic Study on Aminolysis of Y-Substituted-Phenyl Picolinates: Effect of H-Bonding Interaction on Reactivity and Transition-State Structure

  • Kim, Min-Young;Kang, Tae-Ah;Yoon, Jung Hwan;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2410-2414
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    • 2014
  • A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

Kinetic Study on Nucleophilic Substitution Reactions of 4-Nitrophenyl X-Substituted-Benzoates with Potassium Ethoxide: Reaction Mechanism and Role of K+ Ion

  • Kim, Song-I;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.225-230
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    • 2014
  • A kinetic study on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-benzoates (7a-i) with EtOK in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of pseudo-first-order rate constants ($k_{obsd}$) vs. [EtOK] curve upward. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. Hammett plots for the reactions of 7a-i with the dissociated $EtO^-$ and ion-paired EtOK exhibit excellent linear correlations with ${\rho}_X$ = 3.00 and 2.47, respectively. The reactions have been suggested to proceed through a stepwise mechanism in which departure of the leaving-group occurs after the RDS. The correlation of the $k_{EtOK}/k_{EtO^-}$ ratio with the ${\sigma}_X$ constants exhibits excellent linearity with a slope of -0.53. It is concluded that the ion-paired EtOK catalyzes the reaction by increasing the electrophilicity of the reaction center rather than by enhancing the nucleofugality of the leaving group.