• Title/Summary/Keyword: Carbonylation

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Dimethyl Carbonate Synthesis by Methanol Oxidative Carbonylation (메탄올 산화 카르보닐화에 의한 디메틸카보네이트 합성)

  • Nam, Jeong-Kwang;Cho, Deug-Hee;Suh, Jeong-Kwon;Kim, Seong-Bo
    • Korean Chemical Engineering Research
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    • v.49 no.5
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    • pp.530-534
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    • 2011
  • The synthesis of dimethyl carbonate by liquid phase oxidative carbonylation of methanol was studied under batch reaction system. Reaction factors such as effect on various metals, anion containing in copper catalyst, temperature, carbon monoxide and oxygen molar ratio and copper content were investigated. In particular $CuCl_2{\cdot}2H_2O$ showed the excellent of the methanol conversion 65.2%, DMC selectivity 96.6% reaction condition under 1.0 g, $150^{\circ}C$, MeOH/CO/$O_2$=0.2/0.215/0.05 (molar ratio). $CuCl_2$ led to corrosion of the reactor. Thus, a new catalyst system using supports was investigated to resolve these corrosion problem. Influence on various supports were examined and copper catalyst supported on zeolite Y showed the most excellent activity on the formation of dimethyl carbonate. The amount of Fe dissolved during the reaction using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometer) was compared with catalysts, calcined Cu/zeolite Y showed the lower value below 5% than $CuCl_2-2H_2O$.

Effect of Pyridine on Toluene Diisocyanate (TDI) Synthesis Using Direct Carbonylation over Pd/SiO2 (Toluene diisocyanate(TDI) 합성을 위한 Pd/SiO2 촉매상 직접 카보닐화반응에서의 피리딘 첨가효과)

  • Seo, Myung-Gi;Kim, Seongmin;Lee, Dae-Won;Lee, Kwan-Young
    • Korean Chemical Engineering Research
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    • v.50 no.3
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    • pp.417-420
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    • 2012
  • This study is about reduction reaction making 2, 4-dinitrotoluene (2, 4-DNT) to 2, 4-toluene diisocyanate (2,4-TDI) with Pd/$SiO_2$. Catalytic systems based on Pd/$SiO_2$ at about $200^{\circ}C$ and under 100 bars of carbon monoxide. We studied the effect of pyridine on the yield of the TDI. TDI was not created without pyridine, but created with pyridine, at the reaction result. According to research, homogeneous synthesis of TDI with direct carbonylation, palladium and pyridine complexion is known to catalyze. When adding pyridine the reason of TDI synthesis is palladium leaching, ICP-AES was performed to confirm it. As a result, the proportion of Pd loaded in $SiO_2$ was decreased 52% than before, after the reaction by adding 20 vol% pyridine. Generating TDI by adding pyridine might be the effect of the complex ion, which is composed of leached palladium and pyridine.

Photoprotective Effects of Silybum marianum Extract (흰무늬엉겅퀴 열매 추출물의 자외선에 대한 피부 보호 효과)

  • Kim, Daehyun;Bae, Woo Ri;Kim, Yun-Sun;Shin, Dong-won;Park, Sun-Gyoo;Kang, Nae-Gyu
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.45 no.2
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    • pp.209-216
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    • 2019
  • Ultraviolet rays (UV) cause photoaging by inducing skin photodamages such as erythema and sunburn. Silymarin is a mixture of antioxidant polyphenols extracted from Silybum marianum fruit (S. m), which is known as milk thistle. It is known to protect skin tissues from UV treatment and antioxidant effects. In this study, we aimed to identify the photoprotective effects of S. m extract, which has silymarin in the epidermis layer of the skin. We found that the extract can function as a UV filter, so it can reduce DNA damage by UV treatment. Especially, we found that, in the stratum corneum, the extract can suppress the protein carbonylarion and DNA damages caused by suberythemal dose of UV treatment which does not induce erythema in the skin. UV treatment also increased protein carbonylation levels in the stratum corneum by oxidation, but it was prevented by applying the extract. The extract can absorb UV with minimal phototoxicity. Together, our study suggests that S. m extract can be used as a photo-protective ingredient to avoid photoaging of the skin.

Cobalt Catalyzed Carbonylation of Benzal Chloride Derivatives to Alkyl Phenylacetates(II)

  • Shim, Sang-Chul;Doh, Chil-Hoon;Lee, Dong-Yub;Yoon, Young-Zoo;Lee, Seong-Yub;Chae, Shin-Ae;Oh, Hun-Seung
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.20-22
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    • 1992
  • Treatment of benzal chloride, alcohol, $K_2CO_3$, and a catalytic amount of $Co_2(CO)_8$ at $80^{\circ}C$ for 24 hours under 30 atm of CO gave the corresponding alkyl phenylacetate in good yield.

An Efficient Synthesis of$\alpha,\beta-enoyl-\eta^5-(C_5H_5)Fe(CO)(PPh_3)$ Complexes

  • Kwon, Hyok-Boong;Ojima, Iwao
    • Bulletin of the Korean Chemical Society
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    • v.15 no.10
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    • pp.849-852
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    • 1994
  • The ${\alpha},{\beta}$-enoyl chiral iron complexes, ${\alpha},{\beta}-enoyl-{\eta}^5-(C_5H_5)Fe(CO)(PPh_3)$ (1) were prepared from ${\alpha},{\beta}-enoyl-{\eta}^5-(C_5H_5)Fe(CO)_2$(2) and triphenylphosphine through a photochemical ligand substitution followed by carbonylation.

Carbonylation of Benzal Chlorides to Alkyl Phenylacetates using $Fe(CO)_5$

  • Shim, Sang-Chul;Doh, Chil-Hoon;Lee, Sung-Yub;Cho, Chan-Sik
    • Bulletin of the Korean Chemical Society
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    • v.11 no.5
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    • pp.420-422
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    • 1990
  • Various substituted benzal chlorides are converted into alkyl phenylacetates ($ArCH_2COOR$) under CO atmosphere on reaction with a catalytic amount of Fe(CO)$_5$, a base, and an alcohol. The optimum conditions are found as atmospheric pressure of CO, 40$^{\circ}C$, potassium hydroxide as base, and medium of alcohol.

Transition Metal Catalyzed Carbonylation of Nitrobenzene for the Synthesis of N,N'-diphenylurea (균일계 전이금속 촉매를 이용한 니트로벤젠의 카르보닐화 반응 연구: N,N'-디페닐우레아 합성)

  • Lee, Chul Woo
    • Applied Chemistry for Engineering
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    • v.10 no.7
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    • pp.1079-1085
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    • 1999
  • An investigation was made of the effect of various transition metal catalysts, ligands, and a promoter on the synthesis of N,N'-diphenylurea(DPU) from nitrobenzene, aniline, and carbon monoxide. Homogeneous Pd and Ni catalysts were found to be highly efficient, giving almost quantitative isolated DPU yields at 100% nitrobenzene conversion. Bidentate ligand, 1,3-bis(diphenylphosphino)proane(dppp) showed much improved activity and significantly different reactivity relative to the usual monodentate $PPh_3$ ligand in the presence of Ni and Pd catalysts. These results were inferred to the effect of the cis coordination of bidentate dppp ligand on the metal. The use of a promoter $Et_4NCl$ was indispensable in the case of $PPh_3$, yet inhibited the reaction if used with dppp. It was possible to reuse the Pd-dppp catalyst system, although the catalytic activity was reduced slowly.

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Kinetics of Ethyl Phenylcarbamate Synthesis by the Oxidative Carbonylation of Aniline (아닐린의 산화적 카르보닐화에 의한 에틸페닐카바메이트의 합성의 속도론적 고찰)

  • Park, Nae-Joung;Park, Jae-Keun
    • Applied Chemistry for Engineering
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    • v.3 no.4
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    • pp.710-716
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    • 1992
  • Ethylphenyl carbarmate(EPC) was synthesized by oxidative CO carbonylation of aniline in the presence of transition metal catalysts and alkali metal halide cocatalysts at $120^{\circ}C$ under the pressure of 79atm. Oxygen gas was used for oxidizing agent. Kinetics of the reaction was studied and activation energies with different catalysts were estimated. About 100% conversion to EPC and 95% selectivity was obtained in 5 hour reaction. 5% Pd/C was more effective than 5% Rh/C. Effectiveness of cocatalysts was in the order of KI>KBr>KCl. As the temperature increased from $75^{\circ}C$ to $120^{\circ}C$, the conversion rate increased. The reaction was apparent first order and the activation energies with 5% Pd/C and 5% Rh/C were 5.647 and 5.780 kcal/mol, respectively.

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