• 제목/요약/키워드: Catalyst-free

검색결과 269건 처리시간 0.024초

An Improved Protocol on the Synthesis of Thiazolo[3,2-a]pyrimidine Using Ultrasonic Probe Irradiation

  • Tan, Sian Hui;Chuah, Tse Seng;Chia, Poh Wai
    • 대한화학회지
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    • 제60권4호
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    • pp.245-250
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    • 2016
  • An improved protocol on the synthesis of thiazolo[3,2-a]pyrimidine-6-carboxylate derivatives are reported. Previously, the thiazolo[3,2-a]pyrimidine-6-carboxylate derivatives were prepared in a two-step procedure. Under the improved procedure, the thiazolo[3,2-a]pyrimidine-6-carboxylate derivatives was readily prepared in a one-step reaction. This procedure was found to be more efficient than the previous protocol and also compared to the ultrasound bath and conventional heating methods in terms of yield and reaction time.

Very Efficient and Rapid Catalyst-free One-pot Three Component Synthesis of 2,5-Dihydro-5-imino-2-methylfuran-3,4-dicarboxylate Derivatives Under Ultrasound Irradiation

  • Rouhani, Morteza;Ramazani, Ali;Joo, Sang Woo;Hanifehpour, Younes
    • Bulletin of the Korean Chemical Society
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    • 제33권12호
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    • pp.4127-4130
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    • 2012
  • We report a fast, efficient, and facile route for the synthesis of 2,5-dihydro-5-imino-2-methylfuran-3,4-dicarboxylate derivatives from the isocyanide, dialkyl acetylenedicarboxylate and acetic anhydride under ultrasound-assisted conditions. Utilization of easy reaction conditions, very high to excellent yields, and short reaction times makes this manipulation potentially very useful.

Alum Catalyzed Simple and Efficient Synthesis of Bis(indolyl)methanes by Ultrasound Approach

  • Sonar, Swapnil S.;Sadaphal, Sandip A.;Kategaonkar, Amol H.;Pokalwar, Rajkumar U.;Shingate, Bapurao B.;Shingare, Murlidhar S.
    • Bulletin of the Korean Chemical Society
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    • 제30권4호
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    • pp.825-828
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    • 2009
  • Alum $(KAl(SO_4)_2{\cdot}12H_2O)$ is an inexpensive, efficient, non‐toxic and mild catalyst for the synthesis of bis(indolyl)methanes by the reaction of 1H-indole with various aldehydes/ketones under the influence of ultrasound irradiation in solvent‐free condition. The remarkable advantages of this method are the simple experimental procedures, shorter reaction times, high yields of product and green aspects by avoiding toxic catalysts and solvents.

Computational Mechanistic Study on the Catalyst-Free Intramolecular Carbon Insertion

  • 박윤수;정유성
    • EDISON SW 활용 경진대회 논문집
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    • 제2회(2013년)
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    • pp.111-124
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    • 2013
  • Jianbo Wang의 그룹에서 최근 발표한 무촉매 분자 내 탄소-탄소 결합 형성 반응의 메커니즘을 계산 화학적으로 평가한다. 이 반응은 금속 촉매를 사용하지 않는다는 점과 Bio activity 를 갖는 Hydroxy-substituted Polycyclic Aromatic Compound (PAC)를 손쉽게 합성할 수 있다는 점에서 중요하다. Diazo moiety를 갖는 분자의 반응이 일반적으로 진행할 수 있는 세 가지 반응 경로가 제시되었고, DFT functional을 이용해 중간체 및 전이 상태에 대한 최적화 구조 및 에너지를 얻었다. 탄소-탄소 결합의 원천을 탐구하기 위해 Natural bond orbital charge calculation과 치환기 효과에 대한 계산이 수행되었다. 계산 결과, 중간체로 Triplet carbene을 형성하는 경로가 가장 불안정한 중간체를 형성했고, Tosylate가 해리되기 전 탄소-탄소 결합이 형성되는 경로가 가장 합리적인 반응경로임을 알 수 있었다.

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직류 전계하 LLDPE/EVA혼합필름의 절연파괴특성

  • 고시현;김형주;이종필;신현택;이충호;홍진웅
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2000년도 추계학술대회 논문집
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    • pp.65-68
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    • 2000
  • Polyethylene, has long history and is widely used, was researched due to good electrical properties by many authors. But PE under stress has the critical defects of space charge accumulation and tree growth, so various methods such as catalyst, additives and blend to improve these problems have been execute, of which we selected blending method. As in our previous papers we investigated electrical conduction, dielectric and AC dielectric breakdown characteristics, we did DC dielectric breakdown characteristics in this paper. We selected pure LLDPE, pure EVA and LLDPE films mixed with EVA as specimens, which were mixed with the weight percentages of 50, 60, 70 and 80[wt%] to be thin film. DC applying voltage speed was 500[V/sec]. The relation between dielectric breakdown characteristics and the variations of super structure due to mixing was investigated, and especially trap level at amorphous region, threshold energy increment of conductive electron at free volume were considered.

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고속 경질 크롬 도금 용액 개발에 관한 연구 (A study for development of high speed hard chrome plating solution)

  • 추현식;이홍로
    • 한국표면공학회지
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    • 제25권5호
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    • pp.263-269
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    • 1992
  • To enhancing efficiency of hard chrome plating solution more highly, cathode current efficiency were surveyed connected with hardness of deposits, surface morphology, TEM analysis and corrosion test of anode materials. Efficiency war increased up to 26% values by adding catalyst and two kind of additives. With given bath composition and 6$0^{\circ}C$, 60A/d$\m^2$ electrolosis conditionss bright and micro cracked deposits were well obtained, which showed HV 1000 values. From corrosion tests, anode materials such as Pb-Te (0.02%) and Pb-Ag(1%) showed most anti-corrosive results. Through SEM micrograph observations, ef-fects of additives on levelling, brightness and micro crack properties of hard chrome deposits could be con-firmed. Also, through TEM analysis the fact that deposits from crack free solution or high speed solution were more fine than from sargent solution could be confirmed.

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Synthesis of Alternating Head-to-Head Copolymer of Methyl $\alpha$-cyanoacrylate and 2,3-Dihydrofuran. Ring-Opening Polymerization of 3-Methoxy-4-cyano-2,9-dioxabicyclo[4.3.0]non-3-ene

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • 제9권3호
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    • pp.176-179
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    • 1988
  • 3-Methoxy-4-cyano-2,9-dioxabicyclo[4.3.0]non-3-e ne (1) was prepared by (4 + 2) cycloaddition reaction of methyl ${\alpha}$-cyanoacrylate with 2,3-dihydrofuran. Compound 1 was ring-open polymerized by cationic catalyst such as boron trifluoride etherate to obtain alternating head-to-head (H-H) copolymer (2) of methyl $\alpha$ -cyanoacrylate and 2,3-dihydrofuran. For comparison, head-to-tail (H-T) copolymer (3) was also prepared by free radical copolymerization of the corresponding monomers. The H-H copolymer exhibited minor differences in its $^1H$-NMR and IR spectra, but in the $^{13}C$-NMR spectra significant differences were observed between the H-H and H-T copolymers. All of the H-H and H-T copolymers were soluble in common solvents and the inherent viscosities were in the range 0.2-0.3 dl/g.

팜유로부터 바이오디젤 연료를 합성하는 초임계유체반응에서 지방산메틸에스테르의 함량에 미치는 첨가물의 영향 (Effect of Additives on the Contents of Fatty Acid Methyl Esters of Biodiesel Fuel in the Transesterification of Palm oil with Supercritical Methanol)

  • 이홍식;최준혁;신영호;임영섭;한종훈;김화용;이윤우
    • Korean Chemical Engineering Research
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    • 제46권4호
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    • pp.747-751
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    • 2008
  • 수분이나 유리지방산 함량이 높은 폐식용유의 적용 가능성을 알아보기 위하여 초임계메탄올을 이용한 바이오디젤 연료의 합성에서 첨가물이 미치는 영향에 대해 실험하였다. 회분식 반응기를 이용하여 물, 유리지방산, 항산화물질의 함량을 달리하여 전이에스테르화반응을 진행하였고, 기체크로마토그래피를 이용해 시료에 포함된 지방산메틸에스테르의 양을 측정하였다. 수분이 증가함에 따라 생성되는 지방산메틸에스테르의 함량이 약간 감소했으나 염기촉매나 산촉매에 비해서는 그 폭이 아주 작았다. 유리지방산, 비타민 E, ${\beta}$-카로틴의 함량 변화에 따른 영향은 거의 없었다.

Correlation of the Rates of Solvolyses of Cinnamyl Bromide

  • Koo, In-Sun;Cho, Jun-Mi;An, Sun-Kyoung;Yang, Ki-Yull;Lee, Jong-Pal;Lee, I.
    • Bulletin of the Korean Chemical Society
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    • 제24권4호
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    • pp.431-436
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    • 2003
  • Solvolytic rate constants at 25℃ are reported for solvolyses of cinnamyl bromide (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, and 2,2,2-trifluoroethanol. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol. Rate ratios in solvents of the same $Y_{Br}$ value and different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance (e.g. $[k_{40EW}/k_{97TFE}]$Y = 2.88, EW = ethanol-water). With use of the extended Grunwald-Winstein equation, the l and m values are similar to the values of 0.43 and 0.88 obtained for the solvolyses of 1 using the equation (see below) which includes a parameter (I) for solvation of aromatic rings. The magnitude of l and m values associated with a change of solvent composition predicts the $S_{N1}$ reaction mechanism rather than an $S_{N2}$ channel. Product selectivities (S), defined by S = [ether product]/[alcohol product]×[water]/[alcohol solvent] are related to four rate constants for reactions involving one molecule of solvent as nucleophile and another molecule of solvent as general base catalyst. A linear relationship between 1/S and molar ratio of solvent is derived theoretically and validated experimentally for solvolyses of the above substrates from water up 75% 1/S = $(k_{wa}/k_{aw})$([alcohol solvent]/[water]) + $k_{ww}/k_{aw}$ alcohol-water. The results are best explained by product formation from a “free” carbocation intermediate rather than from a solvent-separated ion pair.

Aliphatic Ketone과 Alicyclic Ketone의 Semicarbazone 생성반응에 관한 연구 (Studies on the Semicarbazone Formation of Aliphatic and Alicyclic Ketones.)

  • 임락빈;오양환;김용인
    • 한국응용과학기술학회지
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    • 제8권1호
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    • pp.59-67
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    • 1991
  • The reactions of semicarbazide hydrochloride with aliphatic and alicyclic ketones were studied kinetically at 15, 25, 35 and 45$^{\circ}C$ in 20% ethanol solution buffered at pH 2.9. The rate of cyclohexanone semicarbazone formation is 5.5 times as fast as that of cyclopentanone semicarbazone, while 3-pentanone semicarbazone is 4.7 times as slow as that of 2-pentanone, The activation energy of cyclohexanone, 2-pentanone, 2 hexanone, cyclopentanone, 4-methyl-2-pentanone and 3-pentanone semicarbazone formation are calculated 5.08, 7.52, 8.79, 9.59, 9.49, 11.59, respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ion but neutral molecules being progressed hydrogen bond between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst and concerted nucleophilic attack of free base on the carbonly compound. Dependence on pH of the rate of 2-pentanone semicarbozone formation is linear relationship below pH 4.60 and above pH 5.60. As a result of studing citric acid catalysis, second order constants increase linearly with citric acid concentration. As the catalyst concentration is varied from 0.025 to 0.10 mol/1 at pH 2.90, the rate constants increase 1.4 times, but slight increase is observed at pH 5.60. Conclusively, the rate-determining step is formation of tetrahedral interemediate below pH 4.65 and dehydration between pH 5.60 and pH 7.11. It is concluded that the formation reaction of cyclohexanone semicarbazone is faster than cyclopentanone semicarbazone due to the steric strain in the process of forming tetrahedral intermediate.