• Clean Technology
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• v.28 no.4
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• pp.269-277
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• 2022

With the recent development of the biological enzymatic reaction industry, lactic acid (LA) can be mass-produced from biomass sources. In particular, a catalytic process that converts LA into acrylic acid (AA) is receiving much attention because AA is used widely in the petrochemical industry as a monomer for superabsorbent polymers (SAP) and as an adhesive for displays. In the LA conversion process, NaY zeolites have been previously shown to be a high-activity catalyst, which improves AA selectivity and long-term stability. However, NaY zeolites suffer from fast deactivation due to severe coking. Therefore, the aim of this study is to modify the acid-base properties of the NaY zeolite to address this shortcoming. First, base promoters, Ca ions, were introduced to the NaY zeolites to tune their acidity and basicity via ion exchange (IE) and incipient wetness impregnation (IWI). The IWI method showed superior catalyst selectivity and stability compared to the IE method, maintaining a high AA yield of approximately 40% during the 16 h reaction. Based on the NH₃- and CO₂-TPD results, the calcium salts that impregnated into the NaY zeolites were proposed to exit as an oxide form mainly at the exterior surface of NaY and act as additional base sites to promote the dehydration of LA to AA. The NaY zeolites were further treated with KOH before calcium impregnation to reduce the total acidity and improve the dispersion of calcium through the mesopores formed by KOH-induced desilication. However, this KOH treatment did not lead to enhanced AA selectivity. Finally, calcium loading was increased from 1wt% to 5wt% to maximize the amount of base sites. The increased basicity improved the AA selectivity substantially to 65% at 100% conversion while maintaining high activity during a 24 h reaction. Our results suggest that controlling the basicity of the catalyst is key to obtaining high AA selectivity and high catalyst stability.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2724-2730
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• 2012

A new heterogeneous acidic catalyst was successfully prepared by impregnation of silica (Aerosil 300) by an acidic ionic liquid, named 1-(4-sulfonic acid)butylpyridinium hydrogen sulfate [$PYC_4SO_3H$][$HSO_4$], and characterized using FT-IR spectroscopy, the $N_2$ adsorption/desorption analysis (BET), thermal analysis (TG/DTG), and X-ray diffraction (XRD) techniques. The amount of loaded acidic ionic liquid on Aerosil 300 support was determined by acid-base titration. This new solid acidic supported heterogeneous catalyst exhibits excellent activity in the synthesis of 2-aryl-2,3-dihydroquinazolin-4(1H)-ones by cyclocondensation reaction of 2-aminobenzamide with aromatic aldehydes under solvent-free conditions and the desired products were obtained in very short reaction times with high yields. This catalyst has the advantages of an easy catalyst separation from the reaction medium and lower problems of corrosion. Recycling of the catalyst and avoidance of using harmful organic solvent are other advantages of this simple procedure.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.251.2-251.2
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• 2010

Plant biomass has been proposed to be an alternative source for petroleum-based chemical compounds. Especially, phenolic chemical compounds can be obtained from lignin by chemical depolymerization processes because lignin consists of complex aromatic polymer such as trans-p-coumaryl, coniferyl and sinapyl alcohols, etc. Phenolic chemical compounds from lignin were usually produced in super critical water. However, we applied Near-critical water (NCW) system because NCW is known as a good solvent for lignin depolymerization. Organic matter like lignin can be solved in NCW system and the system has a unique acid-base property without conventional non-eco-friendly chemicals such as sulfuric acid and sodium hydroxide. In this work, we tried to optimize the NCW depolymerization system by adjusting the processing variables such as reaction time, temperature and pressure. Moreover, the amount of additional phenol was optimized by changing the molar ratio between water and phenol. Phenol was used as capping agent to prevent re-polymerization of active fragment such as formaldehyde. Alkali-lignin was used as a starting material and characterized by a Solid State 13C-NMR, FT-IR and EA (Elemental Analysis). GC-MS analysis confirmed that o-cresol, p-cresol, anisole and 4-hydroxyphathalic acid were the main product and they were quantitatively analyzed by HPLC.

• Journal of the Korean Applied Science and Technology
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• v.8 no.1
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• pp.21-26
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• 1991

The rate constants for the addition reaction of thiourea to nitrone derivatives were determind at various pH and reaction rate equation which could be applied over a wide pH were obtained. The substituent effects and general base catalysis for the addition of thiourea to nitrone derivatives were observed. On the basis of these findings, a plausible reaction mechanism for the nucleophilic addition of thiourea to nitrone was proposed.

• Journal of the Korean Chemical Society
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• v.12 no.1
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• pp.35-38
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• 1968

Radio iodination of various aromatic derivatives (aniline, toluene, iodobenzene, acetanilide, benzene, benzoic acid) were achieved at low temperature by a chloroamine-T procedures in presence of polar solvent(dioxane). Organic base (piperidine) was used as the catalyst. Iodine replacement reaction had occured on the aromatic or alicyclic ring by this reaction, and the kind and ratio of iodinated products were proved to be different from those of usual iodide reaction in organic solvent at low temperature. The reactivity of various aromatic or alicyclic compounds towards the present iodination system was evaluated and the scope and limitation of the present procedures in the preparation of radio pharmaceuticals were discussed.

• 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.

• Fibers and Polymers
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• v.3 no.2
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• pp.55-59
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• 2002

The thermal reaction of acetoacetanilide in the presence of aniline or phenol yielded carbanilide in quantitative yields. This reaction was applied to the synthesis of polyurea. Bisacetoacetamides were prepared from diamines and diketene in DMF. They were thermally polymerized in the presence of phenol or a diamine (6FDA) to yield polyureas of low molecular weights. The polymers were soluble in DMSO and NMP. $^1{H-NMR}$ analysis showed that they had amino group terminated structures. Poly(urea-imide) was synthesized by the reaction of an oligourea diamine with pyromellitic dianhydride in NMP. The concentration of terminal amino groups was determined by an acid-base titration. The thermal property of poly(urea-imide) was evaluated by thermogravimetric analysis (TGA). Initial decompisition took place at 332-$350^{\circ}C$.

• Journal of Pharmaceutical Investigation
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• v.20 no.3
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• pp.145-152
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• 1990

Zirconium pyrithione complex was prepared by reaction of sodium-pyrithione solution and zirconyl chloride solution. The physico-chemical properties of the complex was examined by means of IR, XRD, DSC and NMR. And the stability of Zr-complex was investigated on the basis of accelerated stability analysis under conditions of temp. elevation, UV radiation and pH dependence. The result indicates that the ratio of the ligand to metal in Zr-pyrithione complex was determined 4:1, and its stability constant was $4.643{\times}10^4$. The rate order of decomposition of the complex was apparent first-order reaction of which rate constant and the decomposition rate was not only accelerated by effect of heat and UV radiation but was catalyzed by specific acid-base catalysis considered the pH dependence for the hydrolysis of the complex and the suspension was most stable over the range pH 4-8 indicating that solvent catalysis is the primary made of reaction in this region.

• Bulletin of the Korean Chemical Society
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• v.2 no.4
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• pp.132-138
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• 1981

Ab initio molecular orbital calculations have been performed in an effort to determine which types of chemical interactions play essential roles for the system, , $H_2O+CH_2SH^+$, and $H_2O+ CH_2S$. The most important contribution to the interaction energy in controlling reaction path is the exchange repulsion energy, EX, which is largely responsible for the shape of the total interaction energy curve. In the ion-molecule reaction, prior protonation of thioformaldehyde or prior deprotonation of water leads to formation of the corresponding ionic adducts ($H_2O+CH_2SH$ and $HOCH_2S^-$), with no barrier to reaction, simulating specific acid and base catalysis, respectively, as in the case of formaldehyde. Otherwise, approach of water to thioformaldehyde gives rise to a completely repulsive interaction.

• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1613-1619
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• 2011

A hybrid thermosetting maleimido epoxy compound 4-(N-maleimidophenyl) glycidylether (N-MPGE) containing Co(II), Ni(II) and Cu(II) ions was prepared by curing N-MPGE and tetradentate Schiff base Co(II), Ni(II) and Cu(II) complexes. The curing polymerization reaction of N-MPGE with metal complexes as curing agents was studied. The cured samples were studied for thermal stability, chemical (acid/alkali/solvent) and water absorption resistance and homogeneity of the cured systems. The tetradentate Schiff base, 3-[(Z)-2-piperazin-1-yl-ethylimino]-1,3-dihydro indol-2-one was synthesized by the condensation of Isatin (Indole-2, 3-dione) with 1-(2-aminoethyl)piperazine (AEP). Its complexes with Co(II), Ni(II) and Cu(II) have been synthesized and characterized by microanalysis, conductivity, Uv-Visible, FT-IR, TGA and magnetic susceptibility measurements. The spectral data revealed that the ligand acts as a neutral tetradentate Schiff base and coordinating through the azomethine nitrogen, two piperazine nitrogen atoms and carbonyl oxygen.