• Bulletin of the Korean Chemical Society
• /
• 제35권9호
• /
• pp.2673-2678
• /
• 2014

The detailed mechanisms of the efficient $\small{L}$-proline and pyrrolidine catalyzed transamidation of acetamide with benzylamine have been investigated using density functional theory (DFT) calculations. Our calculated results show: (1) the mechanisms of two catalytic cycle reactions are similar. However, the rate-determining steps of their reactions are different for the whole catalytic process. One is the intramolecular nucleophilic addition reaction of 1-COM, the other is hydrolysis reaction of 2-C. (2) COOH group of $\small{L}$-proline is essential for efficient transamidation. The computational results are in good agreement with the experiment finding and mechanism resported by Rao et al. for $\small{L}$-proline-catalyzed synthesis of amidesin good to excellent yields.

• 청정기술
• /
• 제28권3호
• /
• pp.232-237
• /
• 2022

해조류 바이오매스 중 갈조류의 주요 구성 성분인 알긴산은 다양한 산업에서 널리 사용되어지며, 촉매적 저분자화를 통해 당, 당알코올, 퓨란계, 그리고 유기산과 같은 고부가가치 화합물로 전환할 수 있다. 본 연구에서는 루테늄 담지 활성탄과 마그네시아를 혼합하여 알긴산 저분자화 반응에 적용하고자 하였다. 이러한 불균일계 촉매 시스템은 생성물에 대한 분리가 용이하고 정제 과정의 간소화가 장점으로 작용한다. 반응 결과, 탄소 수 5개 이하의 저분자량 알코올 및 유기산이 생성되었으며, 최적의 반응 조건 탐색을 통해 최종적으로 1 wt% 알긴산 수용액 30 mL, 루테늄 담지 활성탄 100 mg, 마그네시아 100 mg, 반응 온도 210 ℃, 반응 시간 1 h의 반응 조건에서 29.8%의 알코올에 대한 탄소 수율과 43.8%의 알코올 포함 액상 생성물에 대한 총 탄소 수율을 확보하였다.

• 공업화학
• /
• 제8권6호
• /
• pp.920-926
• /
• 1997

촉매 글리콜분해공정은 에스테르 교환반응에 의해 생성된 폴리올과 carbamate 화합물을 회수하여 폴리우레탄 폼 제조에 이용하는 화학적 재활용 방법이다. 본 연구에서는 폴리우레탄 폼을 분해하기 위해 ethyleneglycol, diethyleneglycol, 1,4-butanediol을 사용하였으며, 촉매로는 금속 acetate류를 사용하였다. 촉매글리콜분해 반응온도는 $180{\sim}200^{\circ}C$ 범위에서 수행되었다. 반응속도는 반응시간 경과에 따른 생성물의 점도를 측정하여 조사하였으며, IR과 GPC분석을 통하여 분해 생성물의 종류와 분자량 분포를 조사하였다. 촉매 글리콜분해는 높은 온도에서 ethyleneglycol을 사용했을 때 잘되었다. K, Na, Tl acetate 촉매의 활성이 좋았으며, 생성물들은 비교적 높은 함량의 아민화합물과 carbamate화합물을 함유하고 있었다. Sr acetate와 Quinoline 촉매의 경우 반응은 다소 느리지만 폴리올의 함량이 높았고 부생성물의 함량이 낮았다. 회수폴리올을 20wt%까지 첨가하여 제조한 폴리우레탄 폼의 물성이 버진 폴리올만을 사용하여 제조한 폼에 비해 인장강도, 경도, 인열강도, 압축강도 등이 좋았다.

• Bulletin of the Korean Chemical Society
• /
• 제22권3호
• /
• pp.263-266
• /
• 2001

Isopropylation of phenol with 2-propanol has been carried out over Na-exchanged ZSM-5 zeolites to determine the effect of catalyst acidity on phenol conversion and product selectivity. The acid type and strength of the catalyst such as Lewis, weak and strong Bronsted acid sites are measured by pyridine adsorbed XPS and the catalytic properties are interpreted in terms of the acid properties. The active site and mechanism for the reaction are suggested based on evidence of study from the reactant adsorbed FT-IR.

• Journal of Microbiology and Biotechnology
• /
• 제8권5호
• /
• pp.471-477
• /
• 1998

Taq DNA polymerase from Thermus aquaticus is very useful in the polymerase chain reaction. Taq DNA polymerase is classified in the pol I family, represented by E. coli DNA polymerase I. The three-dimensional structural alignment of 3'-5'exonuclease domains from the pol I family DNA polymerases explains why Taq DNA polymerase does not carry out proofreading in polymerase chain reactions. Three sequence motifs, Exo I, II, and III, must exist to carry out 3'-5'exonuclease activity for proof- reading by a 3'-5'exonuclease reaction, but these are abolished in Taq DNA polymerase. The key catalytic module in 3'-5'exonuclease is two metal ions chelated by four active-site carboxylic amino acids. Taq DNA polymerase was mutagenized to construct the catalytic module in the active site. The circular dichroism technique supported the formation of the catalytic module, and the radioactive assay showed that the 3'-5'exonuclease activity doubled in the mutant Taq DNA polymerase.

• Korean Chemical Engineering Research
• /
• 제56권3호
• /
• pp.416-420
• /
• 2018

A comprehensive kinetic study has been conducted on dimethyl carbonate synthesis by transesterification reaction of ethylene carbonate with methanol. An alkali base metal (KOH) was used as catalyst in the synthesis of DMC, and its catalytic ability was investigated in terms of kinetics. The experiment was performed in a batch reactor at atmospheric pressure. The reaction orders, the activation energy and the rate constants were determined for both forward and backward reactions. The reaction order for forward and backward reactions was 0.87 and 2.15, and the activation energy was 12.73 and 29.28 kJ/mol, respectively. Using the general factor analysis in the design of experiments, we analyzed the main effects and interactions according to the MeOH/EC, reaction temperature and KOH concentration. DMC yield with various reaction conditions was presented for all ranges using surface and contour plot. Furthermore, the optimal conditions for DMC yield were determined using response surface method.

• Bulletin of the Korean Chemical Society
• /
• 제32권4호
• /
• pp.1195-1200
• /
• 2011

The catalytic enantioselective Mannich-type reaction promoted by chiral binaphthyl-modified bifunctional organocatalysts is described. The treatment of ${\alpha}$-fluoro-${\beta}$-ketoesters with N-Boc imines under mild reaction conditions afforded the corresponding ${\beta}$-aminated ${\alpha}$-fluoro-${\beta}$-ketoesters with excellent enantioselectivities (up to 98% ee).

• Bulletin of the Korean Chemical Society
• /
• 제8권4호
• /
• pp.329-332
• /
• 1987

The reaction of (E)-1-alkenyl-1,3,2-benzodioxaboroles with a variety of allylic phenoxides in the presence of a catalytic amount of Pd$(PPh_3)_4$ is described. The reaction affords a general and simple procedure for the preparation of 1,4-alkadienes from alkynes via hydroboration.

• Korean Chemical Engineering Research
• /
• 제59권4호
• /
• pp.481-486
• /
• 2021

극초음속 비행체의 비행 중에 발생되는 열 문제를 해결하기 위해 탑재된 연료의 분해반응 시 나타나는 흡열효과를 이용하는 냉각기술이 개발되고 있다. 본 연구에서는 HZSM-5를 촉매로 사용하여 n-dodecane 연료의 분해반응을 수행하였으며, 촉매 분해반응의 흡열효과를 극대화하고 코크생성을 억제하기 위해 촉매를 메탈폼에 코팅하였다. 반응기는 외경 1.27 cm의 스테인리스 스틸 흐름형 반응기를 사용하였다. HZSM-5를 메탈폼에 코팅한 촉매를 사용한 촉매 분해반응 결과 흡열량은 최대 2887 kJ/kg, 기상전환율은 34% 이었으며, 메탈폼의 코크생성량은 촉매를 코팅함에 따라 촉매를 코팅하지 않은 것에 비해 약 56% 감소하였다.

• Bulletin of the Korean Chemical Society
• /
• 제17권11호
• /
• pp.1040-1044
• /
• 1996

The catalytic dehydrocoupling of bis(1-sila-3-butyl)benzene, 1 by Cp2ZrCl2/Red-Al and Cp2ZrCl2/n-BuLi combination catalysts yielded a mixture of oily and solid polymers. While the catalytic dehydrocoupling of 2-phenyl-l,3-disilapropane, 2 by Cp2ZrCl2/n-BuLi combination catalyst produced a mixture of oily and solid polymers, the catalytic redistribution/dehydrocoupling of 2 by Cp2ZrCl2/Red-Al combination catalyst gave oily polymer. The dehydrocoupling of 1 and 2, unless the prior silane redistribution occurs, seems to initially produce a low-molecular-weight polymer, which then undergoes an extensive cross-linking reaction of backbone Si-H bonds, leading to an insoluble polymer.