• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.517-520
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• 1991

The reaction of dichlorophenylvinylsilane with tert-butyllithium in hydrocarbon solvents at room temperature or below generated the Z and E-isomers of 1-chloro-1-phenyl-2-neopentylsilene. The intermediates were trapped by cyclopentadiene, anthracene and methoxytrimethylsilane to give a consistent 90/10 ratio for the Z-silene to E-silene adduct. This result was interpreted as an evidence for stereochemical induction in the silene generation reaction.

• 대한약학회:학술대회논문집
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• 대한약학회 2003년도 Proceedings of the Convention of the Pharmaceutical Society of Korea Vol.2-2
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• pp.183.1-183.1
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• 2003

The synthesis of various cyclic carbamate compounds and amino alcohols has attracted attention in the past because of their potential as antibiotics, antitumor, analgenics, anticonvulsants. Several methods for the preparation of cyclic carbamate compounds have previously been reported including the use of heterocumulenes. We have recently described the novel synthetic method for N-protected amines from various ethers using Chlorosulfonyl isocyanate(CSI) and found that the mechanism of our CSI reaction is a competitive reaction of $S_N1$ and $S_ Ni$ mechanisms according to the stability of carbocation intermediates. (omitted)

• 한국생물공학회:학술대회논문집
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• 한국생물공학회 2005년도 생물공학의 동향(XVII)
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• pp.270-271
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• 2005

• 약학회지
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• 제45권4호
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• pp.321-327
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• 2001

The synthesis of novel taxol analogues with an amine moiety at the 7- and 10-positions to examine the BBB penetration was described. The analogues were synthesized from 2'-O-(tert-butyldim-ethylsilyl)taxol and 2'-0-(tert-butyldimethylsilyl) -7-O-(triethylsilyl)-10-deacetyltaxol, the key intermediates, in 2 steps via the esterification with heterocyclic amino acids and the subsequent desilylation reaction.

• 한국응용과학기술학회지
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• 제22권3호
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• pp.257-269
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• 2005

This study was focused on the maximization of flame-retardancy of polyesters by a synergism of simultaneously introduced chlorine and phosphorus into polymer chains of modified polyesters. To prepare modified polyesters, reaction intermediates, TD-adduct (prepared from trimethylolpropane /2,4-dichlorobenzoic acid (2,4-DCBA)) and TMBO (prepared from tetramethlene bis (orthophosphate)), were prepared first, then condensation polymerization of the prepared intermediates, adipic acid, and 1,4-butanediol were carried out. In the condensation polymerization, the content of phosphorus was fixed to be 2wt%, and the content of 2,4-DCBA that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as ABTTs. The prepared intermediates and modified polyesters were characterized with FT-IR, NMR, GPC, and TGA analysis. Average molecular weight and polydipersity index of the preparation of ABTTs were decreased with increasing 2,4-DCBA content because of the incease in hydroxyl group that retards reaction. We found that the thermal stability of the prepared ABTTs increased with chlorine content at high temperatures.

• 청정기술
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• 제22권4호
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• pp.281-285
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• 2016

난분해성 1,4-다이옥산을 분해시키기 위하여 촉매습식과산화반응에 활성적인 Cu wire촉매를 사용하였다. Cu wire 촉매를 사용함으로써 1,4-다이옥산의 완전한 분해가 가능하였으나, 분해된 1,4-다이옥산은 완전 무기화($CO_2$와 $H_2O$로 전환)되지 못하고 중간생성물인 ethylene glycol diformate, oxalic acid, formic acid, formaldehyde, acetaldehyde 등으로 전환되었다. 1,4-다이옥산이 분해되어 없어짐에 따라 formaldehyde와 oxalic acid가 점진적으로 나타나기 시작하여 증가하다가 최고농도를 보인 후 다시 감소하였다. 이들 두 중간체의 최고농도 도달시점에 acetaldehyde의 농도가 급격히 증가하여 최고농도를 보인 후 다시 감소하였다. 이들 세가지 중간물질의 감소와 함께 ethylene glycol diformate, formic acid가 생성되기 시작하여 그 농도가 점진적으로 증가하였다. 이들은 연속적인 과정을 통해 생성되었다. Cu wire 촉매는 반응이 진행되는 동안 활성이 떨어지지 않고 매우 안정적이었다.

• 한국환경농학회지
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• 제15권2호
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• pp.246-261
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• 1996

현재 사용되고 있는 유기합성 농약의 중요한 부분을 차지하고 있는 유기인계 농약의 대부분은 분자에 황 원자를 포함하고 있으며 환경이나 생체 내에서 대사되어 활성화 되거나 무독화 된다. 이에 관련된 다양한 반응 중 산화반응이 주요 대사반응으로 여겨지는데 이산화대사에 의해 생성된 대사물의 특성도 중요하거니와 반응 중 생성되는 반응성 중간체에 대한 연구는 대사반응의 경로 및 기작 구명에 필수적이고 농약의 독성학적 특성을 이해하는 데에 중요한 위치를 차지하고 있다. 본 총설은 유기인계 농약을 중심으로 관련 유기인 화합물을 대상으로 산화대사 반응 중 생성되는 반응성 중간체에 대한 연구들을 그 구조구명과 반응 기작면에서 다루었다.

• 대한화학회지
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• 제42권2호
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• pp.161-171
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• 1998

알켄-오존 반응에서 생성된 중간 생성물로써 primary ozonide (POZ),secondary ozonide (SOZ)그리고 carbonyl oxide의 분자구조, vibrational frequencies그리고 infrared(IR)스펙트럼의 세기 등에 대한 이론적 연구를 high level ab initio 양자역학적 방법(CISD,CCSD)을 사용하여 수행하였다. 일반적으로, polarization function은 결합각과 결합길이를 감소시키는 경향을 보였고 반면, electron correlation effect는 결합길이와 결합각을 약간 증가시키는 경향을 보이고 있다. Carbonyl oxide의 분자구조는 zwitterionic form이 diradical form보다 더 안정한 것으로 예측되었으며, 두 형태의 에너지는 차이는 TZ2P CISD level에서 약 22.4 kcal/mol인 것으로 계산되었다. 또한, POZ과 SOZ의 분자구조 및 harmonic vibrational frequencies들을 실험결과와 비교 분석하였으며 IR세기에 근거하여 각 vibrational mode를 assign 하였다.

• Journal of Microbiology and Biotechnology
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• 제25권5호
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• pp.704-708
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• 2015

For the analysis of multiple-reaction intermediates for long-chain dicarboxylic acid biotransformation, simple and reproducible methods of extraction and derivatization were developed on the basis of gas chromatography with flame ionization detector (GC-FID) instead of mass spectrometry. In the derivatization step, change of the ratio of pyridine to MSTFA from 1:3 to 9:1 resulted in higher peak intensity (p = 0.021) and reproducibility (0.6%CV) when analyzing 32 g/l ricinoleic acid (RA). Extraction of RA and ω-hydroxyundec-9-enoic acid with water containing 100 mM Tween 80 showed 90.4-99.9% relative extraction efficiency and 2-7%CV compared with those with hydrophobic ethyl acetate. In conclusion, reduction of the pyridine content and change of the extraction solvent to water with Tween 80 provided compatible derivatization and extraction methods to GC-FID-based analysis of longchain carboxylic acids.

• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2719-2723
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• 2012

A kinetic study is reported for nucleophilic substitution reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in MeCN. The plot of pseudo-first-order rate constant ($k_{obsd}$) vs. [amine] curves upward, which is typical for reactions reported previously to proceed through a stepwise mechanism with two intermediates (i.e., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). Dissection of $k_{obsd}$ into the second- and third-order rate constants (i.e., $Kk_2$ and $Kk_3$, respectively) reveals that $Kk_3$ is significantly larger than $Kk_2$, indicating that the reactions proceed mainly through the deprotonation pathway (i.e., the $k_3$ process) in a high [amine] region. This contrasts to the recent report that the corresponding aminolysis of benzyl 2-pyridyl carbonate 5 proceeds through a forced concerted mechanism. An intramolecular H-bonding interaction was suggested to force the reactions of 5 to proceed through a concerted mechanism, since it could accelerate the rate of leaving-group expulsion (i.e., an increase in $k_2$). However, such H-bonding interaction, which could increase $k_2$, is structurally impossible for the reactions of 6. Thus, presence or absence of an intramolecular H-bonding interaction has been suggested to be responsible for the contrasting reaction mechanisms (i.e., a forced concerted mechanism for the reaction of 5 vs. a stepwise mechanism with $T^{\pm}$ and $T^-$ as intermediates for that of 6).