• Title/Summary/Keyword: $S_N2-S_N2'$ Reaction

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Kinetic Study on the Alkaline Hydrolysis of the Substituted Phenyl N,N-diethyl-P-benzylphosphonamidates (치환 Phenyl N,N-diethyl-P-benzylphosphonamidates의 염기성 가수분해 반응에 대한 속도론적 연구)

  • Shon, Kyoung Hwa;Shin, Gap Cheol
    • Journal of the Korean Chemical Society
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    • v.43 no.1
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    • pp.85-91
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    • 1999
  • The second order rate constants for the hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates (2,4-$(NO_2)_2$, 4-$NO_2$, 4-CN, 4-Cl, 4-H)in 20% dioxane-water (v/v) have been determined by UV/Vis spectrophotometric method at various temperatures. The activation parameters (Ea, ${\Delta}H^{\neq}$,${\Delta}S^{\neq}$) were calculated from the rate constants and the reaction constant ($\rho$) was also estimated by Hammett equation. The activation entropies of the title reactions show considerably negative values, this result is not consistent with a dissociative mechanism (EA) in which a positive or a slightly negative value of the entropy of activation should be expected. Further, kinetic evidence for an associative mechanism (AE) was obtained from the linear free energy relationship. By the results of kinetic study for the alkaline hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates, it may be concluded that these reactions proceed through an associative mechanism.

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Substituent Effects for the Menschutkin-Type Reaction of Substituted 2-Phenylethyl arenesulfonates with Substituted Pyridines (치환 2-Phenylethyl arenesulfonate 류와 치환 피리딘류의 Menschutkin 형 반응에 관한 치환기 효과)

  • Soo-Dong Yoh;Joong Hyup Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.413-418
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    • 1989
  • The rates for the reaction of substituted 2-phenylethyl tosylates with substituted pyridines were measured in acetonitrile and that of 2-PNS with substituted pyridines were investigated in both acetonitrile and methanol. The substitutent effect was accelerated by an electron-donating substituent on both substrate and nucleophile. Results showed that More O'Ferrall and quantum mechanical model of predicting transition state structure suggest the reaction proceeds via an $S_N2$ mechanism, in which bond-breaking is more advanced than bond-formation. Transition state variation predicted with the quantum mechanical model is consistent with the experimental results, whereas the predictions provided by the More O'Ferrall plots is found to be inconsistent in leaving group. In the reaction of 2-PNS, the rate constants in acetonitrile were larger than that in methanol.

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Synthesis and Characterization of Poly(arylene ether)s Containing Benzoxazole Pendants from Novel Aromatic Difluoride Monomer

  • Kim, Ji Hyeong;Bang, Sang U;Kim, Yeong Jun
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.896-900
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    • 2000
  • A study was done on the synthesis of new poly(arylene ether)s and poly(arylenesulfide) with rigid benzoxazole pendants using nucleophilic aromatic substitution reaction. As a new aromatic monomer, 1,4-bis(2-benzox-azolyl)-2,5-difluorobenzene [I] w as synthesized in three steps starting from 1,4-dibromo-2,5-difluorobenzene. A model reaction of difluoro monomer [I] with two equivalents of m-cresol or thiophenol in a typical ether con-densation reaction conditions gave very high yields ( > 93%) of the desired disubstituted product, suggesting the feasibility of polymer formation in these reaction system. Monomer[I] was polymerized with bisphenols and bisbenzenethiol in NMP using K2CO3 as base. The molecular weight of the resulting polymers, however,seemed relatively low according to their solution viscosity values ( ηinh = 0.15-0.29 dL/g). The poly(arylene ether)s were soluble in several common organic solvents including chloroform, pyridine and N,N'-dimethylfor-mamide. The poly(arylene sulfide) was, however, ony soluble in strong acids like sulfuric acid and trifluoro-acetic acid. The glass transition temperatures were found to be 175-215 $^{\circ}C.$ These polymers were stable up to 380-420 $^{\circ}C$ in both nitrogen and air, as determined by the temperature that a significant weight loss began to appear on TGA.

Developement of novel enzyme system for production of enantiomerically pure ${\beta}-amino$ acids : Kinetic resolution of racemic 3-amino-n-butanoic acid using transaminase from Alcaligenes denitrificans Y2k-2

  • Im, Seong-Yeop;Jo, Byeong-Gwan;Kim, Byeong-Gi
    • 한국생물공학회:학술대회논문집
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    • 2000.11a
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    • pp.579-582
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    • 2000
  • (R,S)-3-amino-n-butanoic acid$(DL-\;{\beta}\;-homoalanine)$ has been kinetically resolved using Alcaligenes denitrificans Y2k-2 as a biocatalyst, which was isolated from soil by enrichment culture, which was carried out with minimal media containing (R,S)-3-amino-n-butanoic acid as a sole nitrogen source. The enzyme which peformed this kinetic resolution assumed to belong to the ${\omega}-transaminase$ family, because A. denitrificans used pyruvate as amino acceptor and its transaminase activity was inhibited by gabaculine, aminooxy acetic acid and hydroxylamine. In whole cell reaction, (R,S)-3-amino-n-butanoic acid was kinetically resolved to the corresponding (R)-3-amino-n-butanoic acid with excellent E (>100) in the presence of pyruvate as an amino acceptor at $37^{\circ}C$. (S-specific) We observed the substrate inhibition for pyruvate at 100mM. In this study, characteristics of transaminase activity of Alcaligenes denitrificans Y2k-2, such as substrate specificity and thermostability, are carried out for the development of (R)-3- amino-n-butanoic acid production system.

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Nitrogen Removal from Wastewater by a Multi-stage Bio-reactor (다단 생물반응기에 의한 질소제거)

  • 최규철;정일현
    • Journal of environmental and Sanitary engineering
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    • v.13 no.1
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    • pp.91-103
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    • 1998
  • Design data for COD and nitrogen removal from wastewater were collected from Pilot's Multi-stage Bio-reactor. Hyraulic conditions and pollutant loadings were varied in order to optimize the biological and operational parameters. Pilot's experimental results summarize as followings. 1. T-N removal efficiency in the organic volumetric loading 0.2 kgCOD/m$^{3}$·d was obtained as maxium of 85% at internal recycle ratio 2.5 and in more ratio than this it was decreased. Organic removal efficiency was about 91% under the overall experimental conditions and not influenced by recycle ratio.. 2. Nitrification reaction was shown as maxium in the SCOD$_{cr}$/NH$^{+}$-N ratio of 6.5 and in more ratio than this it was decreased. Denitrification rate was the maxium as 85% in more than 7.5 of SCOD$_{cr}$/NO$_{x}$-N ratio and in the ratio over this ratio it becomes constant. 3. By utilizing an applied new model of Stover-Kincannon from Monod's kinetic model, concentration of T-N in the effluent according to flow quanity in the influent was estimated as 8.74 and -67.5 respectively. The formula for estimating T-N concentration of effluent was obtained like this: N$_e$=N$_0$(1- $\frac{8.74}{(QN$_0$/A)-67.05}$)

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The SrLiAl3N4:Eu2+ Phosphor Synthesized by the Raw Material Model Obtained by DFT Calculations

  • Park, Woon Bae
    • Journal of the Korean Ceramic Society
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    • v.54 no.3
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    • pp.217-221
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    • 2017
  • Improvement studies of existing phosphors are needed for use in light emitting diodes (LEDs). Among the phosphors discovered recently, the SLA ($SrLiAl_3N_4:Eu^{2+}$) is a phosphor that has a narrow width. It is now known as a good red phosphor that meets the industry's needs for warm white (color temperature ranging from 2700 to 4000 K) and high CRI (> 80). However, SLA phosphors are obtained from difficult synthetic methods. All commercially available phosphors should be derived from the general solid state synthesis method. The phosphors produced by difficult synthetic methods will inevitably fall out of price competitiveness and will be scrapped. This study succeeded in synthesizing SLA ($SrLiAl_3N_4:Eu^{2+}$) phosphors by using a general solid phase synthesis method based on the reaction energy obtained from DFT calculations. As a result, we found an optimal solid state synthesis method for SLA phosphors.

Synthesis and Characterization of Molybdenum(V) Complexes with Tridentate Schiff Bases

  • Jung Sook Kim;Bon Kweon Koo
    • Bulletin of the Korean Chemical Society
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    • v.13 no.5
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    • pp.507-511
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    • 1992
  • Six-coordinate molybdenum(V) complexes X[MoO$(NCS)_2$(L)], where X=$PyH^+$, $Me_4N^+$, $Et_4N^+$, n-$Bu_4N^+$, and L= the tridentate schiff base dianions derived from the condensation reaction between various salicylaldehydes and 2-aminophenol have been synthesized. The complexes have been characterized by elemental analysis, conductivity, UV-visible, IR, $^1H$-NMR, and mass spectroscopy. The coordination around the molybdenum appears to be distorted octahedral. A tridentate ligand containing the ONO donor atoms occupies meridional positions with the N atom trans to the terminal oxo group. Two NCS ligands bond to the molybdenum through the N atom and are cis to the Mo = $O_t$ group. The electrochemical behaviors of the complexes have also been investigated by cyclic voltammetry in dimethylsulfoxide.

Atomic Layer Deposition of $Sb_2S_3$ Thin Films on Mesoporous $TiO_2$

  • Han, Gyu-Seok;Jeong, Jin-Won;Seong, Myeong-Mo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.282-282
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    • 2013
  • The antimony sulfide ($Sb_2S_3$) thin films were deposited using the gas phase method which known as atomic layer deposition (ALD) on mesoporous micro-films. Tris (dimethylamido) antimony (III[$(Me_2N)_3Sb$] and hydrogensulfide ($H_2S$) were used as precursors to deposit $Sb_2S_3$. Self-terminating nature of $(Me_2N)_3Sb$ and $H_2S$ reaction were demonstrated by growth rate saturation versus precursors dosing time. Absorption spectra and extinction coefficient were investigated by UV-VIS spectroscopy. Scanning electron microscopic analysis and X-ray photoelectron spectroscopy (XPS) depth profile were employed to determine the conformal deposition.

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Eco-Friendly Production Process of N-Hydroxysuccinimide from Succinic Anhydride (Succinic Anhydride로부터 N-Hydroxysuccinimide의 친환경 생산공정 개발)

  • Goo, Bon Suk;Baek, Jeong yeon;Park, Hwa In;Jung, In Chan;Kim, Woo-Sun
    • Clean Technology
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    • v.26 no.2
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    • pp.91-95
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    • 2020
  • A new eco-friendly synthetic method for N-hydroxysuccinimide (NHS), widely used in the pharmaceutical and fine chemical industries, is developed. Conventional synthesis method yields NHS of about 70% after its reaction with NH2OH to succinic acid. In this method, NHS can be obtained using low-cost succinic acid, but a great deal of solvents are required as an extraction method to purify NHS, while the work-up process is complicated, resulting in low yield. In addition, there is a safety risk due to the high reaction temperature for commercial production, and it is not economical due to the high cost of production from the generation of much waste because of an acid catalyst and the use of various solvents. In order to make up for this shortcoming, this study used succinic anhydride as a raw material under low temperature reaction and developed a new eco-friendly industrial synthesis method using isobutyl alcohol for a single solvent and non-catalytic reaction. The economic evaluation confirms that there is a cost reduction effect of about 20%. In the future, based on this result, studies may establish a commercial production technology through scale-up research and proceed with foreign technology transfer.

Sudden unexpected cardio-respiratory arrest after venipuncture in children

  • Jeong, Goun;Shin, Son Moon;Kim, Nam Su;Ahn, Young Min
    • Clinical and Experimental Pediatrics
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    • v.61 no.4
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    • pp.108-113
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    • 2018
  • Purpose: This study aimed to investigate the clinical and socioenvironmental characteristics of sudden cardiorespiratory arrest after venipuncture in children. Methods: We conducted a retrospective email-based survey of all members of the Korean Pediatric Society. The questionnaire included items on patient demographics, socioenvironmental circumstances of the venipuncture, type of cardiorespiratory arrest, symptoms and signs, treatment, prognosis, and presumed cause of the arrest. Results: Fourteen patients were identified. Of these, 13 were young children (<2 years old), and 1 was 14 years old. All patients had been previously healthy and had no specific risk factors for sudden cardiorespiratory arrest. Most cases (n=11, 79%) were defined as cardiac or cardiorespiratory arrest, while the remaining cases (n=3, 21%) were defined as respiratory arrest. Aspiration (n=3), acute myocarditis (n=2), and laryngeal chemoreflex (n=1) were presumed as the causes; however, the exact causes were unclear. The overall prognosis was poor (death, n=7; morbidity, n=5; full recovery, n=2). The medical institutions faced severe backlash because of these incidents (out-of-court settlement, n=5; medical lawsuit, n=5; continuous harassment, n=3). Conclusion: Cardiorespiratory arrest after venipuncture is unpredictable and the probable cause of most cases is a vasovagal reaction. Medical personnel must be aware of the risk of unexpected cardiorespiratory arrest during routine intravenous procedures.