• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.551-555
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• 1999

11-Deoxydaunomycinone 15 and 10-fluoroanthracyclinone derivatives 9, 10 were obtained. Naphthalenone 4 prepared from 2-(2,4-pentadienyl)-1,3-dioxane 2 with methyl vinyl ketone and hydrolysis with HClO4 was condensed with phthalidesulfone 5 through Michael type reaction, and was converted to 7 by epoxidation. Epoxide 7 was transformed to trione 12 using reduction-oxidation or hydrofluorination process, and then to 15 by introducing several functional groups. Compound 8 obtained in the course of the reaction of epoxide 7 and HF/ Pyr was used for the synthesis of compounds 9, 10.

• 대한화학회지
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• 제43권3호
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• pp.294-301
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• 1999

제미널 비스포스폰에이트기를 포함하는 화합물들은 칼슘과 관련된 다양한 질병들 즉 Paget's disease, 악성칼슘과다증, 골다공증등에 약효가 있는 것으로 잘 알려져 있다. 이러한 화합물을 합성하기 위하여 먼저 methylvhyl ketone과 triethylphosphite를 가지고 5배 위된 옥사포스포린 화합물을 합성하였다. 이렇게 합성된 5배위 결합된 옥사포스프린을 bromination, 응용된 Westheimer반응, 그리고 가수분해를 통해서 Y-keto-bisphosphonates를 얻을 수 있었다. 그리고 이 Y-ketobisphosphonates 화합물들은 환원성아민화를 이용해서 N-알킬화된 Y-aminobisphosphonates로 전환하였다. 이렇게 합성된 2차아민 형태의 N-알킬화된 Y-aminobisphosphonates는 N-알킬화반응으로 3차아민을 만든 후 N,N디알킬화된Y-aminobisphosphonates 화합물로 합성할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제16권5호
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• pp.416-421
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• 1995

The approximate rates and stoichiometry of the reaction of excess lithium gallium hydride with selected organic compounds containing representative functional groups were examined under the standard conditions (diethyl ether, 0 $^{\circ}C)$ in order to compare its reducing characteristics with lithium aluminum hydride and lithium borohydride previously reported, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, and amines evolve hydrogen rapidly and quantitatively. However lithium gallium hydride reacts with only one active hydrogen of primary amine. Aldehydes and ketones of diverse structure are rapidly reduced to the corresponding alcohols. Conjugated aldehyde and ketone such as cinnamaldehyde and methyl vinyl ketone are rapidly reduced to the corresponding saturated alcohols. p-Benzoquinone is mainly reduces to hydroquinone. Caproic acid and benzoic acid liberate hydrogen rapidly and quantitatively, but reduction proceeds slowly. The acid chlorides and esters tested are all rapidly reduced to the corresponding alcohols. Alkyl halides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced slowly. Benzonitrile consumes 2.0 equiv of hydride rapidly, whereas capronitrile is reduced slowly. Nitro compounds consumed 2.9 equiv of hydride, of which 1.9 equiv is for reduction, whereas azobenzene, and azoxybenzene are inert toward this reagent. Cyclohexanone oxime is reduced consuming 2.0 equiv of hydride for reduction at a moderate rate. Pyridine is inert toward this reagent. Disulfides and sulfoxides are reduced slowly, whereas sulfide, sulfone, and sulfonate are inert under these reaction conditions. Sulfonic acid evolves 1 equiv of hydrogen instantly, but reduction is not proceeded.

• Bulletin of the Korean Chemical Society
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• 제25권4호
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• pp.533-538
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• 2004

Canonical sampling method has been presented to generate the initial conditions for reactive flux studies of organic reactions in water. Velocity Verlet version of Nose-Hoover chain dynamics algorithm has been employed to sample the initial conditions according to canonical distribution. The unstable normal mode of a transition state has been introduced to define a dividing plane separating reactant and product regions in reaction processes. This method has been implemented and tested for the case iels-Alder reaction of methyl vinyl ketone (MVK) and cyclopentadiene (CPD) in water, providing a reliable tool for further reactive flux molecular dynamics studies in condensed media.

• 약학회지
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• 제48권1호
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• pp.88-92
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• 2004

In this study; a series of 2',4'-doubly branched carbocyclic nucleosides (8,9,10) were synthesized from simple acyclic ketone derivative as starting material. The installation of the 4'-quaternary carbon needed was carried out using a 〔3,3〕-sigmatropic rearrangement. In addition, the introduction of a methyl group in the 2'-position was accomplished by Grig-nard reaction. Bis-vinyl was successfully cyclized using a Grubbs' catalyst II. The natural bases (adenine, cytosine, uracil) were efficiently coupled with the use of a Pd(0) catalyst. Although all the synthesized compounds were assayed against several viruses, only cytosine analogue 9 showed weak antiviral viral activity (EC$_{50}$=45.4 $\mu$M) against CoxB3 virus.s.

• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.483-487
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• 1991

The tetraaza macrocyclic ligand 3,14-dimethyl-2,6,13,17-tetraazatricyclo $[14,4,0^{1.18} ,0^{7.12}]$docosa-2,12-diene(B), that contains two cyclohexane rings, has been prepared as its dihydroperchlorate salt by the nontemplate condensation of methyl vinyl ketone with 1,2-diaminocyclohexane and perchloric acid. Reduction of B with sodium borohydride produces 3,14-dimethyl-2,6,13,17-tetraazatricyclo$[14,4,0^{1.18},0^{7.12}]$docosane(C). Square planar Ni(Ⅱ) and Cu(Ⅱ) complexes of B and C have been prepared by the reaction of the metal ions and the ligands. Synthesis, characterization, and the properties of the ligands and their metal complexes are reported.

• Bulletin of the Korean Chemical Society
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• 제15권3호
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• pp.204-209
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• 1994

Catalytic hydroacylation has been achieved by the reaction of 8-quinolinecarboxaldehyde (1) and various vinyl derivatives such as 2a, 2b and 2c with Wilkinson's complex (3) to give linear alkyl ketones, 4a, 4b and 4c, respectively. However, stoichiometric ligand-promoted hydroacylation of 2a and 2b with [$(C_8H_{14})_2RhCl]_2$ (5) resulted in a mixture of the branched alkyl ketones and the linear alkyl ketones in different ratios. Stoichiometric hydroacylation of some other olefin derivatives such as 6, 11, 12 and 26, produced functionalized alkyl ketone compounds.

• Bulletin of the Korean Chemical Society
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• 제23권9호
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• pp.1218-1242
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• 2002

Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promo te formation of ${\beta}-hydroxyester$, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathways, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type Ⅱ, SET and Paterno-Buchi processes occuring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, ${\beta}-hydroxyester$ synthesis.

• Toxicological Research
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• 제30권3호
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• pp.149-157
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• 2014

Smoking is one of the most serious but preventable causes of cardiovascular disease (CVD). Key aspects of pathological process associated with smoking include endothelial dysfunction, a prothrombotic state, inflammation, altered lipid metabolism, and hypoxia. Multiple molecular events are involved in smoking-induced CVD. However, the dysregulations of reactive oxygen species (ROS) generation and metabolism mainly contribute to the development of diverse CVDs, and NADPH oxidase (NOX) has been established as a source of ROS responsible for the pathogenesis of CVD. NOX activation and resultant ROS production by cigarette smoke (CS) treatment have been widely observed in isolated blood vessels and cultured vascular cells, including endothelial and smooth muscle cells. NOX-mediated oxidative stress has also been demonstrated in animal studies. Of the various NOX isoforms, NOX2 has been reported to mediate ROS generation by CS, but other isoforms were not tested thoroughly. Of the many CS constituents, nicotine, methyl vinyl ketone, and ${\alpha}$,${\beta}$-unsaturated aldehydes, such as, acrolein and crotonaldehyde, appear to be primarily responsible for NOX-mediated cytotoxicity, but additional validation will be needed. Human epidemiological studies have reported relationships between polymorphisms in the CYBA gene encoding p22phox, a catalytic subunit of NOX and susceptibility to smoking-related CVDs. In particular, G allele carriers of A640G and $-930^{A/G}$ polymorphisms were found to be vulnerable to smoking-induced cardiovascular toxicity, but results for C242T studies are conflicting. On the whole, evidence implicates the etiological role of NOX in smoking-induced CVD, but the clinical relevance of NOX activation by smoking and its contribution to CVD require further validation in human studies. A detailed understanding of the role of NOX would be helpful to assess the risk of smoking to human health, to define high-risk subgroups, and to develop strategies to prevent or treat smoking-induced CVD.

• 청정기술
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• 제4권2호
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• pp.54-60
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• 1998

카보닐기를 측쇄에 가지는 폴리페닐비닐케톤(PPVK)과 폴리스티렌(PS)을 블렌드한 후 이 블렌드에 자외선이 조사되었을 때 자외선 조사시간에 따른 광분해성 변화에 대해 연구하였다. 또한 PPVK의 카보닐기중 일부가 수소화된 수소화 폴리페닐비닐케톤(PPVK(H))도 폴리스티렌과 블렌드한 후 광분해성을 조사하여 광분해에 있어서의 카보닐기의 역할에 대해 연구하였다. PPVK의 페닐기가 메틸기로 대치된 폴리메틸비닐케톤(PMVK)도 폴리스티렌과 블렌드된 후 광분해성이 조사되었고 스티렌과 메틸비닐케톤(MVK)을 공중합한 폴리스티렌메틸비닐케톤(SMVK)에 대해서도 광분해성을 측정하여 PS/PMVK 블렌드와 비교하여 보았다. PPVK 또는 PPVK(H)를 PS와 블렌드한 경우의 광분해성은 PPVK를 블렌드한 경우가 PPVK(H)를 블렌드한 경우보다 더 높은 것으로 나타났다. 순수한 PPVK가 PPVK(H)보다 광분해성이 높게 나타난 것으로부터 이는 자연스러운 결과라고 할 수 있겠으며 또한 PPVK(H)는 PPVK의 카보닐기의 일부가 수소화된 고분자라는 점을 감안할 때 이 실험 결과로부터 카보닐기가 광분해에 참여한다는 것을 확인할 수 있었다. 또한 PMVK를 PS에 블렌드 하였을때의 광분해성은 PPVK를 PS에 블렌드한 경우보다 높게 나타났으며 따라서 PS의 광분해를 위하여 비닐케톤 폴리머를 PS에 블렌드할 경우에는 PMVK가 가장 효과적이고 다음으로 PPVK, PPVK(H)의 순서인 것으로 관찰되었다. 또한 스티렌과 메틸비닐케톤을 공중합시킨 SMVK가 PS와 PMVK 블렌드보다 더 높은 광분해성을 보여주어 비닐케톤 폴리머를 PS와 블렌드 시키는 것 보다는 스티렌과 직접 공중합 시키는 것이 더 효과적인 것으로 나타났다.