• Journal of the Korean Chemical Society
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• v.37 no.4
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• pp.423-430
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• 1993

New Palladium(0)-olefin complexes, $(PMe_3)_2Pd{CH_2=C(CH_3)COOH} \;and\;(PMe_3)_2Pd{(CH_3)CH=CHCOOH}$ have been prepared by treating $Pd(PMe_3)_2$(styrene) with methacrylic acid and trans-crotonic acid, respectively. These complexes were characterized by elemental analysis, IR and $^1H-,\;^{13}C-,\;and\;^{31}P$-NMR spectroscopy. The carboxylic acid entity was found non-bonded with palladium while ${\pi}$-bond is formed between the olefin double bond and Pd(0). The results are compared with the metallacycle formation the reaction of Pd(PMe3)2(styrene) with 3-butenoic acid.

• Journal of the Korean Chemical Society
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• v.43 no.1
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• pp.74-84
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• 1999

Most of the reactions involving benzotriazoles as a synthetic auxiliary have been explained by ionic mechanisms, whereas benzotriazole-mediated radical reactions have received little attention. The reaction of 1-[(aryl)(phenylseleno)methyl]benzotriazole with $Bu_3$SnH in the presence of AIBN in benzene at reflux gave 2-aminodiphenyl selenide (16-29%), 2-aminobiphenyl (9-15%), diphenyl diselenide (30-93%), 1-(arylmethyl) benzotriazole (9-39%) and tributyltin-phenyl selenide (10-36%), whereas the compounds were treated with excess molar amount of $Bu_3$SnH in the absence of AIBN to afford N-(arylmethyl)anilines (44-66%) along with diphenyl diselenide (53-100%), benzotriazole (27-35%) and 1-(arylmethyl)benzotriazole (16-33%). Similarly, treatment of 6-aryl-6-(benzotriazol-1-yl)-1-hexenyl phenyl selenides with $Bu_3$SnH in the presence of AIBN gave 6-aryl-6-phenylamino-1-hexene (9-31%) and 1-aryl-1-oxo-5-pentene (15-44%). A mechanism for the formation of the products is proposed.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.14 no.11
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• pp.6000-6007
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• 2013

Cr(VI)-heterocyclic complex[Cr(VI)-isoquinoline] was synthesized by the reaction between of heterocyclic compound(isoquinoline) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-isoquinoline in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene$CH_3$, m-Br, m-$NO_2$). Electron- donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.69(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

• Korean Chemical Engineering Research
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• v.46 no.4
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• pp.769-776
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• 2008

The stereoselective synthesis of chiral terminal epoxide is of immense interest due to their utility as versatile starting materials as well as chiral intermediates. In this study, new chiral Co(salen) complexes bearing cobalt(II) chloride, iron(III) chloride and zinc(II) nitrate have been synthesized and characterized. The mass and EXAFS spectra provided the direct evidence of formation of complex. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of terminal epoxides such as styrene oxide and phenylglycidylether by hydrolytic kinetic resolution technology and for the synthesis of glycidyl buthylate. The easily prepared complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ nucleophile, providing enantiomerically enriched terminal epoxides (>99% ee). The newly synthesized chiral salen showed remakablely enhanced reactivity with substantially low loadings. The system described in this work is very efficient for the sinthesis of chiral epoxide and 1,2-diol intermediates.

• Journal of the Korean Chemical Society
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• v.23 no.6
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• pp.339-348
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• 1979

The kinetics of the solvolysis of 2-furoyl chloride and 2-thenoyl chloride in $MeOH-H_2O,\;EtOH-H_2O,\;(Me)_2CO-H_2O,\;MeCN-H_2O$ and MeCN-MeOH has been investigated. The rates were faster in protic solvents than in aprotic solvents. This was caused by the bond breaking of leaving group through hydrogen-bonding solvation of protic solvents. In MeCN-M$\'{e}$OH the rate in MeOH rich solvents was faster than in MeCN rich solvents by the specific solvation of alcoholic hydrogen and there was a maximum rate of reaction at MeOH mole fraction of 0.8. The reaction rates of solvolysis were considerably slower than those of benzoyl chloride owing to the electron withdrawing effect of thienyl and furyl groups. It was concluded that solvolytic reaction proceeds via a dissociative $S_N2$ mechanism in which bond-breaking precedes bond-formation at the transition state.

• Applied Chemistry for Engineering
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• v.20 no.3
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• pp.279-284
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• 2009

The formation of mesoporous pores in the microporous mordenite crystals was performed by controlled silica extraction on alkaline treatment. Inner tunable mesopore size could be controlled by changing the concentration of alkaline solution. The pore structure of mordenite zeolite was studied by instrumental analysis after alkaline-treatment. To obtain the cage type mesopores, Ti-coating on the ourside mordenite crystals before alkaline treatment was investigated to be the most effective. Polymeric chiral salen Co (III) complexes were successfully encapsulated in mesoporous mordenite zeolite by "ship-in-a-bottle" method. The heterogeneous catalyst could be applied in asymmetric ring opening of epichlorohydrine by water. It showed very excellent enantioselectivity with a high yield in the catalysis.

• Applied Chemistry for Engineering
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• v.26 no.2
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• pp.132-137
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• 2015

BEA-zeolite was modified by alkaline solution to introduce mesoporosity in the crystals and the homogeneous chiral Co(III) salen was immobilized in the mesopores. The dinuclear chiral Co(salen)-$GaCl_3$ catalyst immobilized on mesoporous BEA-zeolite showed high activity for the regioselective ring opening of terminal epoxides by carboxylic acids. Various chiral monoester derivatives could be synthesized with moderate enantioselectivity (47~69 ee%) from racemic epoxides through above reaction. When the chiral (S)-ECH was used as a reactant, it was efficiently resolved by carboxylic acid with a high enantioselectivity in the presence of heterogenized chiral salen catalyst, and the ring opened product afforded optically pure monoester epoxide (R)-GB (up to 98 ee%) through the ring closing in the basic solution by elimination of HCl. The heterogeneous catalyst could be fabricated easily, and the catalytic activity was retained for several times reuse without any further regeneration step.

• Journal of the Korean Chemical Society
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• v.41 no.2
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• pp.88-97
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• 1997

The silyltriflates$(Ph_{3-n}SiH(OTf)_n)$have been produced by the reaction of triphenylsilane and triflic acid$(CF_3SO_3H)$at low temperature. These highly reactive compounds are a valuable reagent for the synthesis of numerous new functional substituted silane derivatives. The reaction of silyltriflates with alkenyl- and alkynylmagnesium bromide as well as organolithium compounds gave new silanes$Ph_2SiHR(R=\;C(CPh,\;CH=CH_2,\;CH_2CH=CH_2,\; (CH_2)_2CH=CH_2,\;(CH_2)_3CH=CH_2)$in high yields. The hydrosilation of prepared alkenyl- and alkynylsilanesPh_2SiHR$in the presence of a platinum catalyst(Pt/C) at high temperature$(200{\circ}C)$gave carbosilane polymers$((Ph_2SiCH=CPh)_n$and$(Ph_2Si(CH_2)m)n;\;m=2∼4, n{\ge}10)$along with five- and six-membered silaalkane ring compounds derived from intramolecular hydrosilation reactions. All of the prepared compounds are confirmed by NMR, UV, IR and mass spectroscopy as well as elemental analysis.

• Journal of the Korean Society of Food Science and Nutrition
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• v.31 no.1
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• pp.21-25
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• 2002

The contribution of lipid to thermal flayer generation from glucose-protein reaction was accomplished by isolating flavor compounds from casein-glucose (CG)and casein-glucose-coin oil (CGL) which were stored for 2 and 4 weeks at 6$0^{\circ}C$ and then reacted at 16$0^{\circ}C$ for 1hr. The volatiles from the reactant mixtures were isolated by a solvent extraction method with methylene chloride and analyzed by gas chromatography and gas chromatography-mass spectrometry. Pyrazine, methylpyrazine, 2,5-dimethylpyrazine, 2-dimethylpyrazine ,2-ethy-5- methyIpyrazine and 2-acetylpyrrole originated from interaction of thermal degradation of casein and lipid oxidation were identified in the CGL samples. It was also found that 3-methyl-1-butanol, 2-cyclopene-1,4-diode, heptanal, nonanal, and 2-heptanone were derived from lipid source. Two additional fatty acids, heptanoic acid and octanoic acid were also identified in the CGL samples. 5-Hydroxymethyl-2-furfural, the most abundant volatile, was responsible for the formation of sugar degradation product. The results suggested that the presence of lipid in the samples had more effect on the contribution of volatile formation of glucose-protein thermal reaction than the absence of lipid in the samples.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.763-767
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• 2019

In this study, thermal decomposition characteristics of exo-tetrahydrodicyclopentadiene (exo-THDCP) composed with a single compound were analyzed by using a flow reactor. The experiments were carried out at $500^{\circ}C$, 50 bar and the products of each flow rate condition were analyzed by using a GC/MS. As a result, it was confirmed that exo-THDCP was decomposed mainly into cyclic compounds and a part was isomerized by heat. As the flow rate was increased, the kinds and ratio of compounds produced through the decomposition and isomerization were decreased. Also, the conversion rate of exo-THDCP and the amount of heat absorbed during the decomposition were also decreased. The compounds rapidly produced by decomposition were mainly formed through the radical form of 1-cyclopentylcyclopentene (1-CPCP) which is one of the intermediates that can be formed from exo-THDCP because it has the lowest activation energy of 42 kcal/mol.