• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1545-1550
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• 2004

meso-Functionalized dipyrromethanes 6-10 were synthesized by acid-catalyzed addition of pyrrole to ${\alpha}$-position of 2-alkenyl pyrroles. The regiochemistry of the reaction can be explained by either the formation of more stable carbocation intermediate or ${\beta}$-addition of ${\alpha},{\beta}$-unsaturated carbonyl compounds. The starting 2-alkenyl pyrroles were synthesized by Aldol condensation of 2-formylpyrrole with active methylene compounds such as nitromethane, diethylmalonate and malononitrile. Attempted ‘2+2' condensation of meso-diethylmalonyldipyrromethane, meso-(p-tolyl)dipyrromethane and p-tolualdehyde afforded three different porphyrins 12, 13 and 14 in reasonable yields. On the other hand, meso-(nitromethyl)dipyrromethane with p-(tbutyl) benzaldehyde resulted in the formation of three different porphyrins such as 5,15-dicyano-10,20-diarylporphyrin (16), 5-cyano-15-formyl-10,20-diarylporphyrin (17) and 5,15-diformyl-10,20-diarylporphyrin (18) in low yields. Conversion of nitromethyl groups to nitrile and (or) formyl group was observed under the porphyrin forming conditions.

• Bulletin of the Korean Chemical Society
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• v.18 no.3
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• pp.274-280
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• 1997

The rates and stoichiometry of the reaction of gallane-trimethylamine with selected organic compounds containing representative functional groups were examined in tetrahydrofuran solution under standardized conditions (THF, 0 ℃). And its reducing characteristics were compared with those of aluminum hydride-triethylamine(AHTEA). The rate of hydrogen evolution from active hydrogen compounds varied considerably with the nature of the functional group and the structure of the hydrocarbon moiety. Alcohols, phenol, amines, thiols evolved hydrogen rapidly and quantitatively. Aldehydes and ketones were reduced moderately to the corresponding alcohols. Cinnamaldehyde was reduced to cinnamyl alcohol, which means that the conjugated double bond was not attacked by gallane-trimethylamine. Carboxylic acids, esters, and lactones were stable to the reagent under standard conditions. Acid chlorides also were rapidly reduced to the corresponding alcohols. Epoxides and halides were inert to the reagent. Caproamide and nitrile were stable to the reagent, whereas benzamide was rapidly reduced to benzylamine. Nitropropane, nitrobenzene and azoxybenzene were stable to the reagent, whereas azobenzene was reduced to 1,2-diphenylhydrazine. Oximes and pyridine N-oxide were reduced rapidly. Di-n-butyl disulfide and dimethyl sulfoxide were reduced only slowly, but diphenyl disulfide was reduced rapidly. Finally, sulfones and sulfonic acids were inert to the reagent under the reaction.

• Journal of Korean Society of Environmental Engineers
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• v.39 no.9
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• pp.542-547
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• 2017

This paper was to analyze the membrane characterization of hydrophilicity, surface morphology and membrane chemical anlysis of three commercial microfiltration/ultrafiltration membranes, and evaluate the filtration performance of a seawater to assess the availability for pretreatment of desalination process. From the results of contact angle, Mem-3, fabricated with polyacrylonitrile, was highly hydrophilic. It find out that Mem-3 has more anti-biofouling property. In Field emission scanning electron microscope (FESEM), Mem-1 (polyethylene) and Mem-2 (Polyvinylidenefluoride) showed the sponge-like shape and Mem-3 showed finger-like shape. Membrane chemical analysis by energy dispersive spectrometer (EDS) presented that Mem-2 was mostly fluoride and Mem-3 had s high ratio of N (32.47%) due to the nitrile group. The permeation flowrate per time on suction pressures using deionized water (D.I. water) tends that permeation rate of Mem-3 more increased when the pressure was increased compared to other membranes. From the results of turbidity and total suspended solids (TSS) removal, turbidity of permeate was 0.191 NTU to 0.406 NTU and TSS was 2.2 mg/L to 3.0 mg/L in all membranes, indicating that it was not suitable for the pretreatment of seawater desalination by short-term experiments.

• Carbon letters
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• v.12 no.1
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• pp.31-38
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• 2011

This study experimentally investigated dicyclohexylammonium 2-cyanoacrylate (CA) as a potential comonomer for polyacrylonitrile (PAN) based carbon fiber precursors. The P(AN-CA) copolymers with different CA contents (0.19-0.78 mol% in the feed) were polymerized using solution polymerization with 2,2-azobis(isobutyronitrile) as an initiator. The chemical structure and composition of P(AN-CA) copolymers were determined by proton nuclear magnetic resonance and elemental analysis, and the copolymer composition was similar to the feeding ratio of the monomers. The effects of CA comonomer on the thermal properties of its copolymers were characterized differential scanning calorimetry (DSC) in nitrogen and air atmospheres. The DSC curves of P(AN-CA) under nitrogen atmosphere indicated that the initiation temperature for cyclization of nitrile groups was reduced to around $235^{\circ}C$. The heat release and the activation energy for cyclization reactions were decreased in comparison with those of PAN homopolymers. On the other hand, under air atmosphere, the P(AN-CA) with 0.78 mol% CA content showed that the initiation temperature of cyclization was significantly lowered to $160.1^{\circ}C$. The activation energy value showed 116 kJ/mol, that was smaller than that of the copolymers with 0.82 mol% of itaconic acids. The thermal stability of P(AN-CA), evidenced by thermogravimetric analyses in air atmosphere, was found higher than PAN homopolymer and similar to P(AN-IA) copolymers. Therefore, this study successfully demonstrated the great potential of P(AN-CA) copolymers as carbon fiber precursors, taking advantages of the temperature-lowering effects of CA comonomers and higher thermal stability of the CA copolymers for the stabilizing processes.

• Journal of Microbiology and Biotechnology
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• v.18 no.3
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• pp.552-559
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• 2008

Ethyl (S)-4-chloro-3-hydroxybutyrate is an intermediate for the synthesis of Atorvastatin, a chiral drug used for hypercholesterolemia. A Rhodococcus erythropolisstrain (No.7) able to convert 4-chloro-3-hydroxybutyronitrile into 4-chloro-3-hydroxybutyric acid has recently been isolated from soil. This activity has been regarded as having been caused by the successive actions of the nitrile hydratase and amidase. In this instance, the corresponding amidase gene was cloned from the R. erythropolis strain and expressed in Escherichia coli cells. A soluble active form of amidase enzyme was obtained at $18^{\circ}C$. The Ni column-purified recombinant amidase was found to have a specific activity of 3.89 U/mg toward the substrate isobutyramide. The amidase was found to exhibit a higher degree of activity when used with mid-chain substrates than with short-chain ones. Put differently, amongst the various amides tested, isobutyramide and butyramide were found to be hydrolyzed the most rapidly. In addition to amidase activity, the enzyme was found to exhibit acyltransferase activity when hydroxyl amine was present. This dual activity has also been observed in other enzymes belonging to the same amidase group (E.C. 3.5.1.4). Moreover, the purified enzyme was proven to be able to enantioselectively hydrolyze 4-chloro-3-hydroxybutyramide into the corresponding acid. The e.e. value was measured to be 52% when the conversion yield was 57%. Although this e.e. value is low for direct commercial use, molecular evolution could eventually result in this amidase being used as a biocatalyst for the production of ethyl (S)-4-chloro-3-hydroxybutyrate.

• Journal of Environmental Health Sciences
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• v.46 no.2
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• pp.159-169
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• 2020

Objectives: The purpose of this study was to investigate changes among the nine kinds of reduction chemical substances in Korea over the period of 2008-2017. We will define basic data for improving the management methods for reducing chemical substances. Methods: A survey of hazardous pollutant emissions for 2008-2017 was conducted through the pollutant Release and Transfer Register homepage. Nine kinds of designated reduction chemical substances (Benzene, Vinyl chloride, Trichloro ethylene, 1,3-butadiene, Dichloro methane, Tetrachloro ethylene, N,N-dimethylformamide, Acrylo nitrile, and Chloroform) provided the study subjects. The emission of hazardous chemicals and health effects used the National Health Statistics and Integrated Chemicals Information System (ICIS) as a reference. Results: Hazardous pollutant emissions increased by 1.2 times over the past decade, and nine types of reduction chemical substances increased by 1.6 times. By region, the emissions of reduction chemical substances over the last 10 years were in the order of Chungbuk, Gyeonggi, and Gyeongbuk. Emissions of Dichloro methane was the highest in Chungbuk and Gyeongbuk. N,N-dimethylformamide was the highest in Gyeonggi. Carcinogen pollutant emissions showed a tendency to increase continuously. In addition, group 1 carcinogen emissions showed a tendency to decrease. Conclusion: In the last decade, the amount of hazardous chemical emissions has been continuously increasing. Hazardous chemical emissions require facility improvement for continuous emissions reduction. More research on reduction of emissions is needed.

• The Korean Journal of Pesticide Science
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• v.2 no.1
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• pp.18-23
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• 1998

In order to obtain leading compound for the development of new pesticide through the organic synthesis of natural products, the synthesis of ricinine, an active compound of Ricinus communis, was established and biological activities of synthetic compounds against insects were examined. The synthetic scheme of ricinine was composed of four steps by the spontaneous condensation of the cyanoacetyl chloride. A modified synthetic process was also estabilshed to enhance the synthetic yield by simple cyclization of ethoxymethylene malononitrile. In the bioassay results of synthetic ricinine and intermediates on four insects, the mortality of ricinine on brown planthopper (BPH, Nilaparvata lugens) and pea weevil(PW, Bruchus rufimanus) was 80% and 75% at the concentration of 1,000 ${\mu}g/ml$ respectively. Chloronorricinine and chlororicinic acid having chloride group in molecular structure gave 60% mortality on two-spotted mite (TSSM, Tetranychus urticae) at the concentration of 500 ${\mu}g/ml$. The mortality of compounds on house mosquito (HM, Culex pipens pallens) was meager at 10 ${\mu}g/ml$ level.

• Elastomers and Composites
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• v.44 no.2
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• pp.122-133
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• 2009

Rubbers, such as natural rubber, polybutadiene, styrene-butadiene rubber, nitrile-butadiene rubber, chlorinated rubber and EPDM, have been continuously improved in response to a heavy demand and a new property requirement from industry. One of the best ways to realize the improvement is the modification of rubbers through chemical reactions, which produce materials with novel properties. In this review, chemical modification reactions of rubbers that contain carbon-carbon double bond units either in their main backbone or as a side group were briefly summarized. The chemical reactions introduce functional groups or functional polymer chains to polymer backbone, which transform a classical rubber to a highly functional material. Especially, we focused on a controlled/"living" radical polymerization techniques, with which a revolutionary broadening of the spectrum of the materials with well defined molecular weight, molecular weight distribution, chain end-functionality and architectures become possible.

• Journal of the Korean GEO-environmental Society
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• v.13 no.6
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• pp.27-31
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• 2012

This study was designed to examine the feasibility of functionalized mesoporous silica as the adsorbent for benzene, toluene, ethylbenzene, and xylene isomers (BTEX) in groundwater. p-Xylene was used as the model compound of BTEX. A series of functionalized mesoporous silica with MCM-41 type of structure was synthesized using a co-condensation method. Monoamine, triamine, nitrile, phenyl, and octyl groups were functionalized to the mesoporous silica structure. Adsorption sites for p-Xylene in a functionalized mesoporous silica were Si-O-Si covalent bond, the surfactant, and the functional group. Octyl-functionalized mesoporous silica with stearyltrimethylammonium chloride as a surfactant showed the highest adsorption ability. The maximum xylene adsorption capacity of the octyl-functionalized mesoporous silica with stearyltrimethylammonium chloride based on Langmuir model was 4.17 mmol/g on $20^{\circ}C$, which was 2.9 times higher than that of MCM-41.

• Journal of Environmental Health Sciences
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• v.21 no.3
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• pp.38-47
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• 1995

The Bioconcentration factor (BCF) is used as an important criterion in the risk assessment of environmental contaminants. Also it can be used as indicator of biomagnification of environmentally hazardous chemicals through food-chain as well as a tool for ranking the bioconcentration potential of the chemicals in the environment. This paper reports the measured BCF value on Chlorothalonil in Carassius auratus(goldfish), under steady state, and examined correlation between the BCF value and the partition coefficient or acute toxicity or physicochemical properties. Carassius auratus(goldfish) was chosen as test organism and test period were 3-day, 5-day. Experimental concentrations were 0.005, 0.01 and 0.05 ppm. Chlorothalonil in fish tissue and in test water were extracted with n-hexane and acetonitrile. GC-ECD was used to detecting and quantitating of Chlorothalonil. Partition coefficient was determined by stir-flask method. $LC_{50}$ was determined on Chlorothalonil. Carbaryl and BPMC. The obtained results were as follows. 1. It was possible to determine short term BCFs of Chlorothalonil through relatively simple procedure in environmental concentrations. 2. $BF_3$ of Chlorothalonil in concentration of 0.005, 0.01 and 0.05 ppm were 2.1866$\pm$0.23446, 3.5269$\pm$0.23517, 10.2045$\pm$0.18053 and BCFs were 6.6543$\pm$0.55257, 6.9774$\pm$0.02500, 23.4576$\pm$2.06884, respectively. 3. Chlorothalonil concentration in fish extract and BCFs of Chlorothalonil were increased as increasing test concentration and prolonging test period. 4. Fate of test-water concentration on Chlorothalonil was greater than that of control-water con-centration. It is considered that greater fate of test-water concentration on Chlorothalonil is due to hydrolyzing nitrile group under the mild condition and substituting chloro group by some aromatic compounds in test water. 5. Determined logP of Chlorothalonil was 2.80. And determined $LC_{50}$ of Chlorothalonil in time of 24, 48, 72 and 96 hr were 0.1684, 0.1402, 0.1400, 0.1352(mg/l) respectively. And $LC_{50}$ of Carbaryl in above times were 19.918, 18.635, 18.466, 18.12(mg/l) respectively. $LC_{50}$ of BPMC were 10.248, 9.166, 9.087, 8.921(mg/l) respectively. 6. It is suggested that the BCF of Carbamates depend on partition coefficients. But BCF of Chlorothalonil, organochlorine pesticide, would be strongly influenced by steric, electronic effect of substituents than partition coefficient.