• Bulletin of the Korean Chemical Society
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• 제21권6호
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• pp.595-603
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• 2000

Ring expansion reactions via endocyclic cleavage of cyclopropylcarbinyl radicals derived from the reaction of [1-benzyloxycarbonylbicyclo[n. 1.O]alk-(n+l)-yl] -1-imidazolethiocarboxylates with tributyltin hydride/AIBN proceeded to produce 3-cycloalkenecarboxylates in good yields. Benzyl (5'-phenoxypentyl) -3-cyclohepten-1 -carboxylate was obtained in 33% yield from the reaction of benzyl 5-methylenebicyclo [4. 1.0]- 1-carboxylates with 4-phenoxybutyl iodide under radical conditions. Selective cleavage of endocyclic bond in cyclopropane to the cyclohexane, results from stabilization of the resultant radical by the carbonyl groups, such as the benzyloxycarbonyl group, which lower the transition state energy for the final cyclopropane cleavage in the ring expansion.

• Archives of Pharmacal Research
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• 제15권3호
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• pp.234-238
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• 1992

Using cell-free extract of Lysobacter lactamgenus, enzymatic conversion of $\delta$-L-($\alpha$-aminoadiphyl)-L-cysteinyl-D-valine (ACV) the first substrate of $\beta$-lactam biosynthesis, into antibiotic compounds was attempted. In high performance liquid chromatographic (HPLC) analysis, the biosynthetic intermediates for cephalosporin antibiotics including isopenicillin N, deacetoxycephalosporin C, deacetylcephalosporin C and unknown cephem compound were detected in reaction mixtures. It implies that cephabacin compounds from L lactamgenus could be produced by biosynthetic routes through penicillin ring formation and its expansion to cephalosporin ring, likely as cephalosporin C from Cephalosporium or cephamycin C from Streptomyces. Among biosynthetic enzyme in cell-free extract, the ring formation activity (isopenicillin N synthetase activity) was separated in 50-60% of ammonium sulfate fraction, and ring expansion activity (deacetoxycephalosporin C synthetase activity) was found to be in 40-50% fraction. The partially purified isopenicillin N synthetase could convert as much as 90% ACV to isopenicillin N during 6-hour reaction.

• 농약과학회지
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• 제9권3호
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• pp.185-190
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• 2005

최초의 침투이행성 농약 살균제, 카르복신 1의 유도체인 16을 고체상에서 합성하였다. 1,3-옥사티올란 유도체를 아실화 반응성을 갖고 있는 4-하이드록시-3-나이트로벤조페논 고체상 6에 연결하여 9를 82%의 수율로 합성하였다. 고체상의 1,3-옥사티올란 9의 황원자를 MCPBA로 산화한 다음 생성된 설폭사이드 10을 산촉매 존재하에서 환팽창하여 상응하는 고체상에 연결된 다이하이드로-1,4-옥사티인 유도체 12를 합성하였다. 고체상의 1,3-옥사티올란 9의 산화물을 p-메톡시아닐린과 반응시켜 1,3-옥사티올란 14, 1,3-옥사티올란 설폰 15, 다이하이드로-1,4-옥사티인 16, 그리고 아세토아세트아닐라이드 유도체 17을 각각 41%, 35%, 14%, 10% 수율로 얻었다.

• 약학회지
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• 제27권3호
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• pp.185-205
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• 1983

Penicillins and cephalosporins are biosynthesized from L-.alpha.-aminoadipic acid, L-cysteine and L-valine. A tripeptide, LLD-$\delta$-($\alpha$-aminoadipyl)cysteinylvaline(LLD-ACV) was isolated from fermentation broths of Cephalosporium acremonium as well as of Penicillium chrysogenum and it was proved that the LL-$\delta$-($\alpha$-aminoadipyl cysteine was formed first in mycelia, to which valine would be connected to give LLD-ACV. However, several points are still unsolved; first, what mechanism is involved in the configurational change from L-valine to D-valine, second, what kind of cyclization mechanism gives a $\betha$-lactam ring and a thiazolidine ring and third, what is the pathways for the ring expansion from penicillins to cephalosporins. At present, it seems clear that LLD-ACV is cyclized to give isopenicillin N, which is transformed to penicillin N and further to cepbalosporin C. Other hydrophobic penicillins, including benzyl penicillin and penicillin V, are formed from isopenicillin N by acyl-exchange reactions catalyzed by penicillin transferase, rather than by acylation reaction on 6-aminopenicillanic acid(6-APA), which was isolated from the fermentation broth of P. chrysogenum and which would be formed by hydrolysis of $\delta-(\alpha$-amincadipyl)amido moiety at the C-6 position in isopenicillin N or penicillin N by penicillin acylase. Acylation of 6-APA is catalyzed also by penicillin acylase, but the reaction is proved not to be involved in penicillin biosynthesis. Understanding the biosynthesis of penicillins and cephalsoporins would provide solutions to increase in fermentation yields of penicillins, especially of cephalosporins and a solution to biological production of 7-aminocepbalosporanic acid (7-ACA) which is of importance in pharmaceutical industry. Still regulation mechanisms in penicillin and cephalosporin biosynthesis are unveiled at all.

• Bulletin of the Korean Chemical Society
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• 제13권1호
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• pp.83-87
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• 1992

The ring expansion of 1,3-thiazolidines 4 derived from ${\beta}$-ketoacid derivatives to the corresponding dihydro-1,4-thiazines 1 by using the action of chlorine on 4 has been achieved. In the chlorinolysis unisolable sulfenyl chlorides 5 may be formed from chlorosulfonium ions 11 by ${\beta}$-elimination involving carbonyl activated methylene hydrogens. Addition of sulfenyl chloride to the internal double bond appears to form probable thiiranium ions 14, which in turn gave 1 with loss of acidic proton. Imminium ions 15 could be hydrolyzed easily to give enol 8. As a side reaction, dihydrothiazine that was formed was further chlorinated to produce dichlorides 16 which were rearranged readily to the chloromethyl compounds 10.

• International Journal of Concrete Structures and Materials
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• 제10권3호
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• pp.337-353
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• 2016

The successful completion of the present research would be achieved using ground waste glass (GWG) microparticles in self-consolidating concrete (SCC). Here, the influences of GWG microparticles as cementing material on mechanical and durability response properties of SCC are investigated. The aim of this study is to investigate the hardened mechanical properties, percentage of water absorption, free drying shrinkage, unit weight and Alkali Silica Reaction (ASR) of binary blended concrete with partial replacement of cement by 5, 10, 15, 20, 25 and 30 wt% of GWG microparticles. Besides, slump flow, V-funnel, L-box, J-ring, GTM screen stability, visual stability index (VSI), setting time and air content tests were also performed as workability of fresh concrete indicators. The results show that the workability of fresh concrete was increased by increasing the content of GWG microparticles. The results showed that using GWG microparticles up to maximum replacement of 15 % produces concrete with improved hardened strengths. From the results, when the amount of GWG increased there was a gradual decrease in ASR expansion. Results showed that it is possible to successfully produce SCC with GWG as cementing material in terms of workability, durability and hardened properties.

• 대한화학회지
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• 제33권2호
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• pp.247-256
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• 1989

4-아세틸-5,6-디히드로-2-메틸-1,4-티아진-3-카르복실산 유도체 24를 상응하는 티아졸리딘 술폭시드의 고리확대에 의하여 제조하였다. 2-메틸-1,3-티아졸라딘-2-아세트산 유도체 12를 산화하여 시스와 트랜스 술폭시드, 14 및 15를 얻었으며 이들의 구조는 수소핵자기 공명스펙트럼, 적외선 흡수스펙트럼, 그리고 중수소 치환반응에 의한 regioselectivity에 근거하여 결정하였다. 산촉매 존재하에서 시스와트랜스 술폭시드, 14 및 15는 중간체 술페닌산 18을 거쳐 디히드로-1,4-티아진 24로 전환되었다. 그러나 중성조건($100^{\circ}C$의 DMF)에서 트랜스 술폭시드 15는 중간체 술페닌산 21을 거쳐 isomeric 디히드로-1,4-티아진 27로 전환하였다. 화합물 24와 27의 생성반응기전도 논의하였다.

• 공업화학
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• 제35권4호
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• pp.309-315
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• 2024

실리콘/탄소(SiC) 복합체는 실리콘의 높은 이론 용량과 탄소 소재의 높은 전기 전도성을 동시에 만족할 수 있어 실리콘 기반 음극의 상용화를 위한 새로운 음극 소재로서 주목받고 있다. 그러나 SiC 활물질의 반복적인 부피 변화에 따른 지속적인 전해질 소모와 용량 감소는 여전히 해결되어야 하는 문제로 여겨진다. 이러한 문제를 해결하기 위해 본 연구에서는 열적 가교 반응을 통해 네트워크 구조를 형성하는 4,4'-methylenebis(cyclohexyl isocyanate) (H₁₂MDI) 기반의 수분산 폴리우레탄 바인더(HPUD)를 제안한다. 가교된 HPUD (CHPU)는 SiC 음극의 건조 공정 중 간단한 열처리를 통해서 가교제인 triglycidyl isocyanurate (TGIC)의 epoxy 고리 개환 반응을 활용하여 제조되었다. 뛰어난 기계적 특성 및 접착 특성을 가지는 CHPU 바인더를 사용한 SiC 음극은 우수한 율속 및 장기 수명 특성을 나타낼 뿐만 아니라, SiC 음극의 부피 팽창 또한 효과적으로 완화시키는 것으로 확인되었다. 본 연구 결과는 가교 구조를 가지는 환경친화적인 바인더가 다양한 실리콘 기반 음극에 활용될 수 있음을 시사한다.

• 대한화학회지
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• 제37권1호
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• pp.119-130
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• 1993

한 분자 내에 3개의 chiral 중심이 있는 1,3-티아졸리딘 술록시드 1의 입체화학을 중수소치환반응 및 trapping 반응을 통해 밝혔다. 3-아세틸-1,3-티아졸리딘 5의 부분이성질체를 분리한 다음 6과 8을 각각 술록시드로 산화시켜 상응하는 $\alpha$-시스 10, $\alpha$-트랜스 11과 $\beta$ -시스 12, $\beta$ -트랜스이성체 13을 얻었다. 술폭시드 10은 중성 조건하의 환류하는 벤젠 또는 톨루엔 용액 중에서 열역학적으로 보다 안정한 13으로 이성질화하였다. 중수소치환반응에 의해서 술폭시드 13과 술폭시드 11의 2-메틸기의 수소원자는 중수소로 치환되었다. 술폭시드 10과 12로부터 sigmatropic 전위에 의해서 생성된 중간체 슬페닌산 25 및 26은 2-머캡토벤조티아졸(2-MBT)에 의하여 trap되어 디술피드 27 및 28로 전환되었으나 동일한 반응조건하에서 술폭시드 11 및 13은 환팽창 생성물 디히드로-1,4-티아진 29로 전환되었다. 산촉매 존재하에서 술폭시드 10, 11, 12는 술폭시드 13을 통해서 디히드로-1,4-티아진 29로 정량적으로 전환되었다. 술폭시드들의 이성질화 및 29의 생성메카니즘도 기술하였다.