• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.1834-1838
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• 2012

A facile route for the synthesis of dimethyl glutarate (DMG) from cyclobutanone and dimethyl carbonate (DMC) in the presence of solid base catalysts has been developed. It was found that the intermediate carbomethoxycyclobutanone (CMCB) was produced from cyclobutanone with DMC in the first step, and then CMCB was further converted to DMG by reacting with a methoxide group. The role of the basic catalysts can be mainly ascribed to the activation of cyclobutanone $via$ the abstraction of a proton in the ${\alpha}$-position by base sites, and solid bases with moderate strength, such as MgO, favor the formation of DMG.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.141-146
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• 2014

A series of bimetallic Cu-Zn/$SiO_2$ catalysts were prepared via thermal decomposition of the as-synthesized $CuZn(OH)_4(H_2SiO_3)_2{\cdot}nH_2O$ hydroxides precursors. This highly dispersed Cu-solid base catalyst is extremely effective for hydrogenation of ethyl acetate to ethanol. The reduction and oxidation features of the precursors prepared by coprecipitation method and catalysts were extensively investigated by TGA, XRD, TPR and $N_2$-adsorption techniques. Catalytic activity by ethyl acetate hydrogenation of reaction temperatures between 120 and $300^{\circ}C$, different catalyst calcination and reduction temperatures, different Cu/Zn loadings have been examined extensively. The relation between the performance for hydrogenation of ethyl acetate and the structure of the Cu-solid base catalysts with Zn loading were discussed. The detected conversion of ethyl acetate reached 81.6% with a 93.8% selectivity of ethanol. This investigation of the Cu-Zn/$SiO_2$ catalyst provides a recently proposed pathway for ethyl acetate hydrogenation reaction to produce ethanol over Cu-solid base catalysts.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2257-2262
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• 2014

$C_{60}$ is widely investigated because of its unique structure. But its applications in solid propellant seem to be relatively neglected. $C_{60}$ has more outstanding features than carbon black which is widely used as a catalyst ingredient of solid propellant. To combine the advantages of fullerene and lead salts, another good composite in propellant catalysts, we synthesized a kind of fullerene phenylalanine lead salt (FPL) and explored its thermal performances by differential thermal analysis (DTA) and thermogravimetry analysis (TGA). The results show it undergoes four exothermic processes started from 408 K. Combined TGA and X-ray diffractometer (XRD), the decomposition mechanism of FPL was derived by TG-IR and comparing IR spectra of FPL and its residues after burned to $327^{\circ}C$, $376^{\circ}C$ and $424^{\circ}C$, respectively. Effect of FPL on the decomposition characteristic of hexogen (RDX), a type of explosive in propellant, has been investigated using DTA at different heating rate, which shows the decomposition temperatures of the explosive are all reduced by more than 20 K. The corresponding activation energy ($E_a$) is decreased by $30kJ{\cdot}mol^{-1}$. So FPL has potential application as a combustion catalyst in solid propellant.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1590-1600
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• 2014

Cinchona-based bifunctional catalysts have been extensively employed in the field of organocatalysis due to the incorporation of both hydrogen-bonding acceptors (quinuclidine) and hydrogen-bonding donors (e.g., alcohol, amide, (thio)urea and squaramide) in the molecule, which can simultaneously activate nucleophiles and electrophiles, respectively. Among them, cinchona-derived (thio)urea and squaramide catalysts have shown remarkable application potential by using their bifurcated hydrogen bonding donors in activating electrophilic carbonyls and imines. However, due to their bifunctional nature, they tend to aggregate via inter- and intramolecular acid-base interactions under certain conditions, which can lead to a decrease in the enantioselectivity of the reaction. To overcome this self-aggregation problem of bifunctional organocatalysts, we have successfully developed a series of sulfonamide-based organocatalysts, which do not aggregate under conventional reaction conditions. Herein, we summarize the recent applications of our cinchona-derived sulfonamide organocatalysts in highly enantioselective methanolytic desymmetrization and decarboxylative aldol reactions. Immobilization of sulfonamide-based catalysts onto solid supports allowed for unprecedented practical applications in the synthesis of valuable bioactive synthons with excellent enantioselectivities.

• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.689-698
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• 1991

Activated oxidation catalysts are generated by the treatment of pentadentate Schiff base cobalt(Ⅱ) complexes with the oxygen saturated DMF solution. Oxidation of 2,6-di-tert-butylphenol by homogeneous oxidation catalysts of superoxo type pentadentate schiff base cobalt(Ⅲ) complexes yields 2,6-di-tert-butylbenzoquinone(BQ) as a major product. And $O_2$/Co mole ratio of homogeneous oxidative catalysts such as [Co(Ⅲ)(sal-DET)]$O_2$ and [Co(Ⅲ)(sal-DPT)]$O_2$by PVT method of the oxygen absorption in DMSO and pyridine solution was 1:1, 1:1.52 in DMF solution and ${\mu}$-peroxo type cobalt(Ⅲ) complexes formed at solid state. The redox reaction processes of superoxo type cobalt(Ⅲ) complexes as homogeneous oxidation catalysts were investigated by cyclic voltammetry and DPP method at a glassy carbon electrode. As a result of electrochemical measurements the reduction processes of oxygen adducted superoxo type cobalt(Ⅲ) complexes occurred to four steps including prewave of $O_2$-in 0.1M TEAP-DMSO and 0.1 M TEAP-Pyridine as supporting electrolyte solution.

• Bulletin of the Korean Chemical Society
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• v.29 no.11
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• pp.2202-2204
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• 2008

• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.417-423
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• 2006

A series of amine functionalized MCM-41 catalysts were prepared by aminopropyltrimethoxysilane grafting and their catalytic performance in Knoevenagel reaction of selected substrates was investigated. Water resistant and catalytically active amine grafted MCM-41 was prepared by post-synthetic silylation using methyltrimethoxysilane ; hydrogen bonding of the water molecules formed during the condensation reaction to the active N group was suppressed, which led to high TON of the reaction. Amine functionalized MCM-41 prepared by coating method produced high conversion, but the TON of the catalyst was much lower than that of the amine grafted MCM-41; pore volume of the functionalized MCM-41 decreased substantially and large portion of the immobilized amine is believed to be hydrogen bonded to each other, which can result in decrease in the basicity of the N group. A secondary amine group was prepared by room temperature condensation between aminopropylsilane and chloropropylsilane, and the MCM-41 grafted with the secondary amine group demonstrated the highest catalytic activity among the catalysts prepared.

• Korean Journal of Materials Research
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• v.5 no.5
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• pp.620-624
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• 1995

To study the acid and base properties of chemical-treated natural zeolite, FT-IR analysis was performed by the adsorption of pyridne and pyrrole and thermo-gravimetric analysis was done by the adsorption of NH$_{3}$. These solid catalysts have two acid sites, which are related to the Bronsted and Lewis acid sites, respectively. HIC-treatment led to the increased acidity and the maintained basicity.Acidity of NaHO-treatment samples also increased with thr NaOH-treatment but basicity decreased. The p-xylene selectivity on the chemical-treatment zelite was higher than that on the untreated zeolite.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.715-720
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• 1993

Diphenylmethane (pKa=33.4), which is difficult to be oxidized in normal oxidation conditions, was oxidized to produce benzophenone at ambient temperature and atmospheric pressure by using phase transfer catalysts and solid potassium tert-butoxide as base. Quaternary salt such as benzyltriethylammonium chloride, tetrabutyl ammonium bisulfate, tetrabutylphosponium chloride, are ineffective catalysts for this reaction, but 18-crown-6 and polyethylene glycols showed catalytic activity. The conversion of diphenylmethane was increased with increasing chain length of PEG molecules when they are used as phase transfer catalysts both in equal molar and equal weight basis. The conversion of diphenylmethane was increased with the agitation speed, and aprotic solvent like DMF showed higher reaction rate compared with benzene.

• Clean Technology
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• v.19 no.3
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• pp.313-319
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• 2013

To produce biodiesel efficiently from fish oil containing 4% free fatty acid, esterification and trans-esterification were carried out with Vietnam catfish oil, which was kindly provided from GS-bio company. Heterogeneous solid acid catalysts such as Amberlyst-15 and Amberlyst BD-20 and sulfuric acid as homogeneous acid catalyst were used for the esterification of free fatty acids in the fish oil. Sulfuric acid showed the highest removal efficiency of free fatty acid and the shortest reaction time among three acid catalysts. The base catalysts for trans-esterification such as KOH, $NaOCH_3$ and NaOH were compared with each other and KOH was determined to be the best transesterification catalyst. Some solid material, which assumed to be saponified product from glycerol and biodiesel, were observed to form in the fish oil biodiesel when using $NaOCH_3$ and NaOH as the transesterification catalyst. The initial acid value of fish oil was proven to have a negative effect on biodiesel conversion. Of the three catalysts, KOH catalyst transesterification was shown to have high content of FAME and the optimal ratio of methanol/oil ratio was identified to be 9:1.