• 대한화학회지
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• 제58권1호
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• pp.44-48
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• 2014

Catalytic performance of Lewis acids have been investigated in the synthesis of 1,2,3,4-tetrahydroquinolines via cyclocondensation reaction of aniline derivatives with cyclic enol ethers such as 3,4-dihydro-2H-pyran and 2,3-dihydrofuran. The catalytic activity of various of these catalysts in different solvents was compared with other classical catalysts such as KSF clay (1.5 g), $InCl_3$ (10-20 mol%), $ZrOCl_2$ (10 mol%), $Sc(OTf)_3$ (3 mol%), PANI-$InCl_3$ (10 mol%), $I_2$ (20 mol%), $InCl_3$ (5 mol%), 4-npa (25 mol%) and Cellulose-$SO_3H$ (0.03 g).

• Bulletin of the Korean Chemical Society
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• 제33권6호
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• pp.1939-1944
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• 2012

Benzoyloxy benzophenone derivatives were prepared in 3 steps including DCC coupling, Fries rearrangement and esterification from benzoic acids in 24-89% total yields. Among the prepared 12 benzophenone analogues 1a-1l, the compound 1b having three chloro groups at the para position showed maximum inhibitory effects of ICAM-1 expression but, 1a which have no substituents at all showed no inhibitory activity. This study provides the evidences that benzoyloxy benzophenone derivative, 1b may exert its anti-inflammatory activity by suppressing IFN-${\gamma}$-induced ICAM-1 expression.

• Archives of Pharmacal Research
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• 제14권4호
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• pp.364-369
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• 1991

The synthesis and regioselective reactions of a chiral allyl sulfide. (S)-(+)-(1-methylpyrrolidin-2-yl)methyl allyl sulfide (MAS, 1) are described. Remarkable ${\alpha}-regioselectivity$ was observed in the alkylation of the carbanion of MAS while 1:3 mixtures of ${\alpha}-and\;{\gamma}-adducts$ were produced in the addition of the MAS anion to aldehydes. However, a dramatic change of the regioselectivity was witnessed when Lewis acids such as $Et_3Al$, $Et_3B$, and $Ti(O^iPr)_4$ were used as additives in the addition reaction. In these cases, ${\alpha}-adducts$ were formed exclusively. A rationale for the change of regioselectivity is provided. And the stereochemical aspect of the addition reaction is also described.

• Bulletin of the Korean Chemical Society
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• 제21권9호
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• pp.860-866
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• 2000

Hydrocarbostyril, which is a key intermediate in our new synthetic route to 6-nitroquipazine, can be prepared from 1-indanone oxime by Beckmann rearrangement. We have optimized the reaction by using a Lewis acid, aluminum chloride,in the yield of 91% instead of common acids such as polyphosphoric acid,and sulfuric acid used in conventional Beckmann rearrangement (20% in the literature, 10% in our experiment).The optimized condition is established by usingthree equivalents of aluminum chloride in CH2Cl2 at -40 $^{\circ}C$ - room tempera-turefor 40 min. We have applied this condition to other 1-indanone derivatives, such as 4-methyl-, 4-methoxy-, 4-nitro and 6-nitro-1-indanones. The mechanism ofthis BR has been proposed on the basis of the effect of tem-perature and substituenton product ratio, with the aid of PM3 calculation for a model system.

• Bulletin of the Korean Chemical Society
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• 제11권6호
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• pp.543-546
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• 1990

N- vs. S-Substitution reactions of 1-substituted tetrazoline-5-thiones with various allyl or benzyl halides were studied in order to find effective conditions for N-substitution reactions. When allyl or benzyl halides were reacted with 1-substituted tetrazoline-5-thiones in the presence of TMSI or $BF_3{\cdot}OEt_2$ (or other Lewis acids), N-substitution at 4-position in addition to S-substitution occurred. Reactions were performed either with or without a solvent such as dioxane or propionitrile in the presence of potassium iodide.

• Reproductive and Developmental Biology
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• 제36권3호
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• pp.193-198
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• 2012

This study was to examine expression of the recombinant full-length adiponectin (recombinant adiponectin) in insect ovarian cell culture system and to characterize structural properties of the recombinant adiponectin secreted in medium. Gene construct encoding the recombinant adiponectin contained N-terminal collagen-like domain (110 Amino Acids, AAs), C-terminal globular domain (137 AAs) and C-terminal peptides for detection with V5 antibody (26 AAs included adaptor peptide) and purification using the 6xHis tag (6 AAs). The approximate molecular weight of the product (monomer) was 35 kDa. Molecular mass species of the expressed recombinant adiponectin were monomer (~35 kDa), dimer (~70 kDa), trimer (~105 kDa) and hexamer (~210 kDa). The major secreted species were the LMW forms, such as monomer, dimer, and trimer. There was MMW of hexamer as minor form. HMW multimers (~300 kDa) were shown as a tracer or not detected on the SDS-PAGE in several experiments (data not shown). The multimer forms in this study were not compatible to those in animal or human serum and adipose tissue by other researcher's study in which the major multimer forms were HMW. By protein denaturing experiments with reducing reagent (${\beta}$-MeOH), anionic detergent (SDS) and heat ($95^{\circ}C$) on the SDS-PAGE, not all adiponectin multimers seemed to have disulfide bond linked structure to form multimers. The recombinant adiponectin which expressed in insect ovarian cell culture system seemed to have the limitation as full physiological regulator for the application to animal and human study.

• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.311-317
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• 2003

Vanadium oxides supported on zirconia and modified with MoO₃were prepared by adding Zr(OH)₄powder into a mixed aqueous solution of ammonium metavanadate and ammonium molybdate followed by drying and calcining at high temperatures. The characterization of prepared catalysts was performed using FTIR, Raman spectroscopy and solid-state $^{51}V$ NMR. In the case of a calcination temperature of 773 K, for samples containing low loading of $V_2O_5$, below 15 wt %, vanadium oxide was in a highly dispersed state, while for samples containing high loading of $V_2O_5$, equal to or above 15 wt %, vanadium oxide was well crystallized because the $V_2O_5$ loading exceeded the formation of a monolayer on the surface of $ZrO_2$. The $ZrV_2O_7$ compound was formed through the reaction of $V_2O_5\;and\;ZrO_2$ at 873 K and the compound decomposed into $V_2O_5\;and\;ZrO_2$ at 1073 K, which were confirmed by FTIR spectroscopy and solid-state $^{51}V$ NMR. IR spectroscopic studies of ammonia adsorbed on $V_2O_5-MoO_3/ZrO_2$ showed the presence of both Lewis and Bronsted acids.

• 대한화학회지
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• 제31권2호
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• pp.133-142
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• 1987

시클로로펜타디엔과 메틸기로 치환된 알렌의 산 및 에스테르간의 (4+2)고리화반응에서 입체 선택성을 $\pi$-비결합상호작용($\pi$-NBI)을 적용하여 고찰하였다. 열반응에서는 diene(LUMO)-dienophile (HOMO)만을 고려한 2-FMO방법이, 산촉매반응에서는 diene (HOMO)-dienophile (LUMO)상호작용만을 고려한 2-FMO방법이 이들의 입체선택성의 결정에 중요하였다. cumulated diene계의 친디엔체에서 메틸 치환기는 알렌구조와 through-bond 상호작용에 의해 $\pi$-isoconjugate diene 구조를 형성하여 컨쥬게이션기로 작용하며 FMO의 에너지에 narrowing effect를 주고 있으나 이같은 $\pi$-isoconjugated diene 구조를 만들 수 없는 친디엔체에서는 메틸기가 단순히 전자주는기로 작용한다. 열반응에서 입체선택성은 에틸렌 분자와 마찬가지로 메틸 치환기의 $\pi$-비결합 2차궤도 상호작용($\pi$-NSOI)에 의해서 좌우되었다.

• 공업화학
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• 제8권3호
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• pp.425-429
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• 1997

윤활유 첨가제 중간체인 polyisobutenylsuccinic anhydride(PIBSA)를 polyisobutylene(PIB)과 maleic anhydride(MA)을 이용하여 합성하였다. PIB-a와 MA의 결합반응은 각각의 이중결합사이의 반응을 통하여 이루어지는데 반응조건에 따른 결합도를 측정하였다. 용매를 사용하지 않고 $190^{\circ}C$로 12시간 반응한 경우는 결합도가 0.98을 보였으며 같은 온도에서 벤질알코올 용매를 사용한 경우는 0.21, 그리고 루이스 산촉매인 $AlCl_3$ 및 $SnCl_4$, $Et_2AlCl$, $TiCl_4$을 사용한 경우는 0.03~0.20을 보였다. 또한 PIB의 종류에 따라 결합도의 차이를 보였다. MA의 결합도는 PIB에 ${\alpha}$-올레핀(ego)형이 많이 포함될 수록 증가함을 확인하였다. PIB과 MA가 결합된 PIBSA의 구조는 FT IR과 $^1H$ NMR을 통하여 결정하였다. 결합된 MA의 anhyhide IR 흡수대가 1782 및 $1855cm^{-1}$에서 강하게 나타나며, 1639 및 $897cm^{-1}$에서 보인 PIB의 이중결합의 흡수대가 사라진 것으로부터 알 수 있다. $^1H$ NMR을 통하여 결합된 MA를 확인하는 것은 상대적으로 anhydride peak의 양이 적어 거의 불가능하지만, 확대된 5.5~2.5영역에서 PIB과 다른 peak를 확인할 수 있다. 제조한 PIBSA와 diaminoethane를 반응시키어 윤활유첨가제인 polyisobutenylsuccimide(PIBSI)을 제조하였다.