• Journal of the Korean Chemical Society
• /
• v.27 no.6
• /
• pp.441-448
• /
• 1983

A wide variety of vinylic bromides such as (Z)-1-bromopropene, 1-bromo-2-methylpropene, 2-bromo-3-methyl-2-butene, (E)-ethyl 2-methyl-3-bromo-2-propenoate, 1-bromo-cyclohexene has been found to react with ethyl acrylate, ethyl 3-butenoate, allyl cyanide, (E)-ethyl crotonate, ethyl 4-pentenoate, methyl 10-undecenoate and methyl methacrylate in the presence of triethylamine and a palladium acetate-triorthotolylphosphine catalyst. In general, 2,4-dienoic acid derivatives were obtained in good yield and stereochemistry of the products was determined. Using this method, four, five and eleven carbon-carbon extension with ethyl 3-butenoate, ethyl 4-pentenoate and methyl 10-undecenoate was also possible.

• Journal of the Korean Chemical Society
• /
• v.27 no.4
• /
• pp.255-261
• /
• 1983

Several new $[Pd(L)X_2]$ complexes have been prepared with aminophosphines (L) such as trans-1,2-bis[diphenylphosphino)amino]cyclohexane and 1,2-bis[(diphenylphosphino) amino] propane that contain phosphorus atom as ${\pi}$-electron acceptor, and the bond character of complexes have been investigated by means of infrared and electronic spectroscopy. It was found that thiocyanate ions are N-coordinated possibly due to the steric and electronic influence of the phosphorus atom in aminophosphines that formed seven-membered chelate rings, and that spectrochemical series that is derived from the electronic spectra of the complexes is $NCS^- > Cl^- > Br^- > I^-$

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.20 no.5
• /
• pp.207-215
• /
• 2010

This study was carried out for the purpose of obtaining the basic data for identifying the origin of amethyst. For this, the three dimensional shapes of inclusions contained in various amethyst were observed with Stereo Zoom microscope. The shape and chemical composition of cross section of solid inclusion and the chemical composition of evaporite were investigated by SEM-EDS. The evaporite is made from evaporating of liquid inclusion which is flowed out of amethyst sample by decompressing. Lastly, The trace mineral composition of amethyst was investigated by ICP-AES after digesting the amethyst sample with HF-$H_2SO_4$ solution.

• Journal of the Korean Chemical Society
• /
• v.36 no.4
• /
• pp.598-602
• /
• 1992

2-Piperidylglycine will be a model compound for the synthesis of antitumor agent 593A. 2-Piperidylglycine may be synthesized by alkylation of glycine equivalent to C-2 position of piperidine ring. ${\delta}$-Valerolactam was reacted with trimethyl oxonium tetrafluoroborate to give 2-methoxy-1-piperideine. The imino ether was not condensed with ethyl phthalimidoacetate, one of glycine equivalents, but with ethyl nitroacetate to afford ethyl nitro-2-piperidylene acetate. The subsequent hydrogenation over Pt/C gave ethyl 2-piperidyl glycinate. Because the Z-configuration of the condensed product was assigned by nmr, the stereochemistry of ethyl 2-piperidyl glycinate different from that of Agent 593A.

• Prospectives of Industrial Chemistry
• /
• v.24 no.6
• /
• pp.3-18
• /
• 2021

가역적인 표면 젖음성의 제어가 가능한 스마트 표면은 첨단 센서, 기능성 멤브레인 등 여러 산업분야에 적용될 수 있는 계면제어 기술로써 많은 관심을 받을 것으로 기대된다. 표면의 젖음성은 표면의 화학적 구조와 기하학적 입체 구조에 의해 영향을 받는 데, 특히 외부자극에 의해 소재 물성을 가변시킬 수 있는 스마트 고분자 소재를 나노구조가 제어된 표면에 도입함으로써 표면의 젖음성을 초발수에서 초친수로 가역적으로 전환시킬 수 있는 스마트 표면을 효과적으로 구현할 수 있다. 자극 응답성 스마트 소재는 인가하는 외부자극에 따라 물리적 자극(빛, 온도, 전기, 자기)과 화학적 자극(pH, 용매, 이온)으로 구분할 수 있으며, 이를 복합적으로 적용한 이중/다중 유발 자극에 반응하는 소재가 있다. 본 기고문에서는 외부자극에 응답하는 자극응답성 고분자를 나노 구조 표면에 도입하여 초발수에서 초친수로의 가역적인 젖음성 변화가 가능한 고기능성 스마트 표면의 최근 연구 동향과 미래 전망에 대해 소개하고자 한다. 이런 다양한 외부자극을 이용한 표면 특성의 가역적 제어 기술을 통해 물-오일의 분리, 바이오센서, 약물 전달, 소프트로보틱스와 같은 스마트 소재의 잠재적 발전 가능성 또한 엿볼 수 있을 것으로 기대된다.

• Journal of the Korean Chemical Society
• /
• v.55 no.4
• /
• pp.594-602
• /
• 2011

The effect of ${\alpha}$-, ${\beta}$- and ${\gamma}$-picolines on the stereochemistry of the coordination compounds of lanthanide(III) nitrates derived from 4[N-(furfural)amino]antipyrine semicarbazone (FFAAPS) has been studied. The general composition of the present coordination compounds is [Ln(FFAAPS)$(NO_3)_3$Pic] (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy or Ho and Pic=${\alpha}$-, ${\beta}$- or ${\gamma}$-picolines). All these coordination compounds have been characterized by elemental analyses, molecular weight, molar conductance, magnetic susceptibility, infrared and electronic spectra. The infrared studies suggest that the FFAAPS behaves as a neutral tridentate ligand with N, N, O donor while ${\alpha}$-, ${\beta}$- or ${\gamma}$-picoline is coordinated to the lanthanide(III) ions via heterocyclic N-atom. Nitrates are bicovalently bonded in these compounds. From the electronic spectral data, nephelauxetic effect (${\beta}$), covalence factor ($b^{1/2}$), Sinha parameter (${\delta}%$) and the covalence angular overlap parameter (${\eta}$) have been calculated. Thermal stabilities of these complexes have been studied by thermogravimetric analysis. The coordination number of lanthanide(III) ions in the present compound is found to be ten. The antibacterial studies screening of the primary ligand FFAAPS and the complexes showed that the present complexes have moderate antibacterial activities.

• Applied Chemistry for Engineering
• /
• v.26 no.1
• /
• pp.111-115
• /
• 2015

Two new analogs of bestatin were prepared from $\small{D}$-leucine and $\small{D}$-valine in a stereoselective and efficient way. An aminopeptidase inhibitor bestatin shows significant biological effects on immunomodulation and is marketed for the treatment of acute myelocytic leukemia. The key intermediates, trans-oxazolidine methyl esters 2a and 2b, were obtained with more than 20 to 1 stereoselectivity in a one-pot procedure by the three cascade reactions between N-hydroxymethyl protected ${\alpha}$-amino aldehydes (4a and 4b) and phenylsulfonylnitromethane ($PhSO_2CH_2NO_2$) and the following in-situ ozonolysis. Basic hydrolysis of 2a and 2b, and then the peptide coupling with $\small{L}$-Leu-OMe produced the protected derivatives of two new bestatin analogs, 3a and 3b, respectively. The new isobutyl and isopropyl analogs of bestatin (1a and 1b) were produced in overall 51% and 38% yields, respectively, with high stereoselectivity from the corresponding protected ${\alpha}$-amino aldehydes 4 in a six-step process.

• Analytical Science and Technology
• /
• v.5 no.3
• /
• pp.239-247
• /
• 1992

The complexations and selectivities of the 10 species of mono- and dimethylsubstituted anilinium ions with 18-crown-6 in methanol are examined at dropping mercury electrode. The stability constants of these complexes varies drastically due to the steric hindrance by the positions and numbers of methyl groups. And the analyses of the isomeric mixtures of methylanilinium, which are impossible to detect due to the overlapped peaks in normal conditions, were also accomplished by the additions of 18-crown-6 as the supporting complexing agent using the selective complexations by the steric hindrance effects. As results in case of the difference of stability, ${\Delta}log\;K$ were about 0.7~1.3, it was possible to confirm the existence of two species qualitatively. Otherwise when ${\Delta}log\;K$ were large than 1.6, the quantitative determinations of each species could be accomplished sucessfully. From these results it is deduced that the selective recongnition of the positions and numbers of methyl groups as the steric hindrance in anililniums by 18-crown-6 cause the large variation of the magnitudes of negative shift of reduction waves for guest ions in mixtures.

• Applied Chemistry for Engineering
• /
• v.25 no.4
• /
• pp.392-395
• /
• 2014

(2S,3S,4S)-3,4-Dihydroxyglutamic acid (DHGA), a biologically active ${\alpha},{\beta}$-dihydroxy-${\gamma}$-amino acid, was efficiently synthesized from a readily available D-serine derivative in 30% overall yield over 11 steps. The key stereoselective $OsO_4$-catalyzed dihydroxylation reaction controlled by an N-diphenylmethylene group on the amino group of ${\gamma}$-amino-${\alpha},{\beta}$-unsaturated (Z)-ester successfully introduced the diol moiety of the intermediate 5a in 86% with more than 10 : 1 diastereomeric ration. Then it was in turn successfully converted to the desired target compound, (2S,3S,4S)-3,4-DHGA, via simple oxidation and hydrolysis in a highly stereoselective manner and a higher yield than the previous syntheses. This result strongly supports that our synthetic methodology of stereoselective $OsO_4$-catalyzed dihydroxylation should be useful in stereoselctive synthesis of various bioactive compounds with an amino diol moiety.

• Radiation Oncology Journal
• /
• v.27 no.4
• /
• pp.189-193
• /
• 2009

Purpose: To report on the changes in the patterns of care and survival over time for esthesioneuroblastoma. Materials and Methods: We retrospectively analyzed 42 previously untreated and histologically confirmed esthesioneuroblastoma patients seen between March 1989 and June 2007. According to Kadish's classification, 3 patients (7%) were stage A, 6 (14%) at stage B, and 33 (79%) at stage C. Of the 33 Kadish C patients, 19 and 14 patients were treated from 1989 through 2000 and from 2001 through 2007, respectively. Treatment included surgical resection, radiotherapy, chemotherapy, or a combination of these methods. Chemotherapy was administered to 8 of 19 patients (42%) seen from 1989 through 2000, whereas all of the 14 patients seen from 2001 through 2007 received chemotherapy (p<0.001). No patient was treated by three-dimensional conformal radiotherapy (3D-CRT) from 1989 through 2000, however 8 of 14 patients (67%) seen from 2001 through 2007 underwent 3D-CRT (p<0.001). The median follow-up time for surviving patients was 6.5 years (range, 2.2~15.8 years). Results: The 5-year overall survival (OS) and progression-free survival (PFS) rates for the entire cohort were 53% and 39%, respectively. The 5-year OS was 100% for Kadish stages A or B and 39% for stage C (p=0.007). For patients with stage C disease who were treated from 1989 to 2000 and from 2001 to 2007, the 5-year OS rate was 26% and 59% (p=0.029), respectively and the corresponding 5-year PFS rate was 16% and 46% (p=0.001), respectively. Intraorbital extension and treatment era (1989~2000 vs. 2001~2007) were found as independent factors for OS and PFS in a multivariate analyses. Conclusion: The results of this study suggest that treatment era, which features a distinction in treatment modality and technique with the introduction of 3D-CRT, may be the cause of improved OS and PFS in Kadish stage C patients. To achieve better outcomes for patients with Kadish stage C, combined chemoradiotherapy, especially 3D-CRT, is recommended in addition to surgery.