• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1621-1627
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• 2010

The investigation of the catalytic activity of supported rhodium(I) complex [Rh(P-S)$(CO)_2$] (P-S; polymer anchored salicylic acid) toward the reductive carbonylation of nitrobenzene in DMF medium has been reported. Use of basic cocatalysts in the reaction medium enhanced the percentage of more useful phenyl carbamates. Spectroscopic studies indicate that the reaction proceeds through a dimer species [Rh(HS)(CO)(C(O)$OCH_3$)(${\mu}-OCH_3)]_2$ and phenyl isocyanate is formed as an intermediate. A plausible reaction mechanism based on the identification of reactive intermediates from the soluble rhodium variety has been proposed for the carbonylation process.

• YAKHAK HOEJI
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• v.52 no.6
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• pp.514-519
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• 2008

We developed a convenient synthetic route to 3-alkylated 2-phenyl-4-quinolone derivatives (4a-h and 5a-c), which were expected to retain antitumor activity. A series of 2,3-dihydro-2-hydroxy-2-phenyl-4-quinolones (3a-h) was synthesized through dehydration, dealcoholation and hydration using acid-catalyzed one-pot reaction from anilines and ethyl benzoylacetates. 3-Methyl (or 3,3-dimethyl)-2-phenyl-4-quinolone derivatives 4 and 5 were synthesized from 3a-h through the methylation using methyl iodide. Formation of quinolone nucleus was undertaken with p-toluenesulfonic acid (p-TSA) at $90{\sim}110^{\circ}C$ in toluene for 3${\sim}$7.5 hr over the Dean-Stark apparatus. The key intermediates in these preparations are ${\beta}$-ketoesters 2a-h, which can be readily obtained from the corresponding anilines 1a-e by reaction with ethyl bezoylacetates.

• Bulletin of the Korean Chemical Society
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• v.1 no.2
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• pp.45-49
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• 1980

During the homolytic reactions of $CCl_4$ or $Cl_3CBr with ${\beta}-halo^1$-styrenes,$\beta$-haloradicals are key intermediates. They are to be stabilized via three pathways; $\beta$-cleavage, halogen transfer and telomerization. The three reaction paths are delicately controlled by the energetics of their formation and stabilization. When the formation of a $\beta$-haloradical is accompanied by considerable excess of energy from an exothermic reaction, $\beta$ -cleavage is often dominant over the halogen transfer. On the other hand, if the radical forms via a reversible reaction, two processes become competitive. $\beta$-Eliminated bromine atoms from ${\beta}$ -bromoradicals generate $Br_2$ via $Cl_3CBr + {\cdot}Br {\leftrightarrow} Br_2 + {CCl_3}{\cdot}{Br_2}$ may act as a better scavenger than Cl3CBr for the ${\beta}$-bromoradicals. Different reactivities of chlorine, bromine and trichloromethyl radicals towards olefinic pi-bond are clarified in terms of the beat content of the addition reactions.

• Journal of Korean Society on Water Environment
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• v.18 no.4
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• pp.411-419
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• 2002

In this study, the series of ultrasonic irradiation for removal of refractory aromatic compounds has been selected as a model reaction in the batch reactor system in order to obtain the reaction kinetics. The products obtained from the ultrasonic irradiation were analysed by GC and GC/MSD. The decomposition of benzene produced toluene, phenol, and C1-C4 compounds, while the intermediates during the ultrasonic irradiation of 2,4-Dichlorophenol(DCP) were phenol, HCl, catechol, hydroquinone, and benzoquinone. It was found that more than 80% of benzene, and 2,4-DCP solutions were removed within 2 hours in all reaction conditions. The reaction order in the degradation of these three compounds was verified as pseudo-zero or first order. From the fore-mentioned results, it can be concluded that the refractory organic compounds could be removed by the ultrasonic irradiation with radicals, such as $H{\cdot}$ and $OH{\cdot}$ radical causing the high increase of pressure and temperature. Finally, it appeared that the technology using ultrasonic irradiation can be applied to the treatment of refractory compounds which are difficult to be decomposed by the conventional methods.

• Journal of the Korean Society of Industry Convergence
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• v.15 no.3
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• pp.71-77
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• 2012

This study gives the optimal reaction conditions, reaction mechanisms, reaction rates leaded from the oxidation of phenol by electron beam accelerator and ozone used for recent water treatment. It gives the new possibility of water treatment process to effectively manage industrial sewage containing toxic organic compounds and biological refractory materials. The high decomposition of phenol was observed at the low dose rate, but at this low dose rate, the reaction time was lengthened. So we must find out the optimal dose rate to promote high oxidation of reactants. The reason why the TOC value of aqueous solution wasn't decreased at the low dose was that there were a lot of low molecular organic acids as an intermediates such as formic acid or glyoxalic acid. In order to use both electron beam accelerator and biological treatment for high concentration refractory organic compounds, biological treatment is needed when low molecular organic compounds exist abundantly in sewage. In this experiment, the condition of making a lot of organic acids is from 5 kGy into 20 kGy dose. Decomposition rate of phenol by electron beam accelerator was first order reaction up to 300ppm phenol solution on the basic of TOC value and also showed first order reaction by using both air and ozone as an oxidants.

• Journal of Microbiology and Biotechnology
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• v.25 no.11
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• pp.1810-1818
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• 2015

For the synthesis of various pharmaceuticals, chiral alcohols are useful intermediates. Among them, (R)-ethyl-4-chloro-3-hydroxybutanoate ((R)-ECHB) is an important building block for the synthesis of L-carnitine. (R)-ECHB is produced from ethyl-4-chloro-3-oxobutanoate (ECOB) by a reductase-mediated, enantioselective reduction reaction. The Saccharomyces cerevisiae YOL151W reductase that is expressed in Escherichia coli cells exhibited an enantioselective reduction reaction toward ECOB. By virtue of the C-terminal His-tag, the YOL151W reductase was purified from the cell-free extract using Ni²⁺-NTA column chromatography and immobilized onto Ni²⁺-magnetic microparticles. The physical properties of the immobilized reductase (Imm-Red) were measured using electron microscopy, a magnetic property measurement system, and a zeta potential system; the average size of the particles was approximately 1 μm and the saturated magnetic value was 31.76 emu/g. A neodymium magnet was used to recover the immobilized enzyme within 2 min. The Imm-Red showed an optimum temperature at 45℃ and an optimum pH at 6.0. In addition, Bacillus megaterium glucose dehydrogenase (GDH) was produced in the E. coli cells and was used in the coupling reaction to regenerate the NADPH cofactor. The reduction/oxidation coupling reaction composed of the Imm-Red and GDH converted 20 mM ECOB exclusively into (R)-ECHB with an e.e._p value of 98%.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2324-2328
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• 2007

Organic fluorine chemistry produces many useful products. This paper elucidates the reaction of ethyl-4,4- difluoro-2-iodo-5-oxo-5-phenylpentanoate (2) with primary amines in a one-pot scheme. The reaction produced a series of β-fluoropyrrole derivatives at ambient temperatures. In this reaction, the less bulky the primary amine the higher was the resultant yield. When (2) and aqueous methylamine (40%) were allowed to react below 0 oC, 5-(ethoxycarboxyl)-1-methyl-3,3-difluoro-2-hydroxy-2-phenylpyrrolidine, an intermediate molecule for 2-ethyl-4-flouro-1-methyl-5-phenylpyrrole-2-carboxylate (5), was isolated first. Then, (5) reacted with hydroperchloric acid and acetic anhydride to form 5-(ethoxycarboxyl)-1-methyl-3,3-difluoro-2- phenylpyrrolinium perchlorate (6), which was converted to 2-ethyl-4-flouro-1-methyl-5-phenylpyrrole-2- carboxylate gradually in the presence of a base. Our experiments demonstrate that the formation of 2-ethyl-4- flouro-1-methyl-5-phenylpyrrole-2-carboxylate occurs via both one-pot schemes and stepwise pathways, depending on the reaction conditions. The isolation and characterization of the isolated intermediate (6) suggest an anionic pathway for this reaction.

• Journal of Life Science
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• v.14 no.1
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• pp.17-20
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• 2004

Effects of monovalent cations were examined on the fast $\beta$reaction of $\alpha$D56N and $\alpha$D56G mutant tryptophan synthase. Reaction rates for the production and degradation of intermediates in the reaction were changed in the presence of cathons. The mutant proteins showed different reaction rates from those of wild-type protein, and additional changes occurred in the presence of cations. The results showed that monovalent cations and $\alpha$D56 are important in allosteric properties of this protein.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1573-1578
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• 2009

A computational study of the reactions between Zn-containing species, the products of the thermal decomposition of diethylzinc (DEZn) and water was investigated. The Zn-containing species – $C_2H_5)_2,\;HZnC_2H_5,\;and\;(ZnC_2H_5)_2$ – were assumed to react with water during ZnO metal organic chemical vapor deposition (MOCVD). Density functional theory (DFT) calculations at the level of B3LYP/6-311G(d) were employed for the geometry optimization and thermodynamic property evaluation. As a result dihydroxozinc, $Zn(OH)_2$, was the most probable reaction product common for all three Zn-containing species. A further clustering of $Zn(OH)_2$ was investigated to understand the initial stage of ZnO film deposition. In experiments, the reactions of DEZn and water were examined by in-situ Raman scattering in a specially designed MOCVD reactor. Although direct evidence of $Zn(OH)_2$ was not observed, some relevant reaction intermediates were successfully detected to support the validity of the gas phase reaction pathways proposed in the computational study.

• Advances in Energy Research
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• v.4 no.2
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• pp.177-187
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• 2016

Ammonia borane $NH_3BH_3$ solubilized in organic solvent is a potential liquid-state chemical hydrogen storage material. In this study, metal acetylacetonates like $Fe(O_2C_5H_7)_3$, $Co(O_2C_5H_7)_2$, $Ni(O_2C_5H_7)_2$, $Pd(O_2C_5H_7)_2$, $Pt(O_2C_5H_7)_2$ and $Ru(O_2C_5H_7)_3$ are considered for assisting dehydrocoupling of ammonia borane in diglyme (0.135 M) at $50^{\circ}C$. The molar ratio between ammonia borane and metal acetylacetonate is fixed at 100. A protocol for the separation of the soluble and insoluble fractions present in the slurry is proposed; it consists in using acetonitrile to make the precipitation of metal-based compounds easier and to solubilize boron-based intermediates/products. The nature of the metal does not affect the dehydrocoupling mechanisms, the $^{11}B\{^1H\}$ NMR spectra showing the formation of the same reaction intermediates. The aforementioned metal acetylacetonates do mainly have effect on the kinetics of dehydrocoupling. Dehydrocoupling takes place heterogeneously and dehydrogenation of ammonia borane in these conditions leads to the formation of polyborazylene via intermediates like e.g., B-(cyclodiborazanyl) amine-borane and borazine. Our main results are reported and discussed herein.