• 제목/요약/키워드: halides

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혼합용매에서의 용매화 (제 5 보) : 메탄올-아세톤 혼합용매계에서 tert-Butyl Halides와 1-Adamantyl Tosylate의 가용매 분해반응

  • 이익춘;나상무;공병후;이본수;손세철
    • 대한화학회지
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    • 제31권1호
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    • pp.25-30
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    • 1987
  • 메탄올-아세톤 혼합용매에서 tert-butyl halides와 1-adamantyl tosylate 가용매 분해반응과 메탄올-클로로포름 혼합용매계에서 tert-butyl bromide의 가용매 분해반응을 연구하였다. 메탄올-아세톤 혼합용매의 이온화 능력의 척도를 구하였으며 기질의 변화에 따른 Y값의 변화를 논의하였다. 메탄올-아세톤 혼합용매계의 Y값은 1-adamantyl tosylate를 이용하여 구한 값이 가장 좋은 결과를 줌을 알 수 있었으며 용매에 의한 이탈기의 OTs > Cl > Br > I순서로 커짐을 알 수 있었다.

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Indium and Gallium-Mediated Addition Reactions

  • Lee, Phil-Ho
    • Bulletin of the Korean Chemical Society
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    • 제28권1호
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    • pp.17-28
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    • 2007
  • Indium and gallium have emerged as useful metals in organic synthesis as a result of its intriguing chemical properties of reactivity, selectivity, and low toxicity. Although indium belongs to a main metal in group 13, its first ionization potential energy is very low and stable in H2O and O2. Therefore, indium-mediated organic reactions are of our current interest. On the basis of these properties of indium, many efficient indium-mediated organic reactions have been recently developed, such as the addition reactions of allylindium to carbonyl and iminium groups, the indium-mediated synthesis of 2-(2-hydroxyethyl)homoallenylsilanes, the indiummediated allylation of keto esters with allyl halides, sonochemical Reformatsky reaction using indium, the indium-mediated selective introduction of allenyl and propargyl groups at C-4 position of 2-azetidinones, the indium-mediated Michael addition and Hosomi-Sakurai reactions, the indium-mediated β-allylation, β- propargylation and β-allenylation onto α,β-unsaturated ketones, the highly efficient 1,4-addition of 1,3-diesters to conjugated enones by indium and TMSCl, and the intramolecular carboindation reactions. Also, we found gallium-mediated organic reactions such as addition reactions of propargylgallium to carbonyl group and regioselective allylgallation of terminal alkynes.

Stoichiometric Solvent Effect on SN1 Solvolytic Reactivity Accounting for Phenomenon of Maximum Rates in Methanol-Nitromethane Mixtures

  • Ryu, Zoon-Ha;Choi, Su-Han;Lim, Gui-Taek;Sung, Dea-Dong;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • 제25권9호
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    • pp.1346-1350
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    • 2004
  • Pseudo-first order rate constants $(k_{obs})$ are reported for the following solvolyses in approximately isodielectric mixtures: 3- and 4-methoxybenzyl chloride, bromo- and chlorodiphenylmethane, and 4-chloro-, 4,4'-dichloro and 4-methyl-chlorodiphenylmethane in 0-80% v/v nitromethane-methanol mixtures; and bromo- and chlorodiphenylmethane and 4-methyl-chlorodiphenylmethane in various acetonitrile-methanol mixtures (in the range 0-50% v/v) at$25^{\circ}C.$ These data, and literature data for t-butyl halides (Cl, Br, and I), and for p-methoxybenzoyl chloride, show rate maxima in solvent compositions of ca. 30% aprotic cosolvent, explained by a stoichiometric solvent effect on electrophilic solvation. Linear relationships are observed between $(k_{obs})/[MeOH]^2$ and [AP]/[MeOH], where [AP] refers to the molar concentration of aprotic cosolvent. The results are consistent with competing third order contributions to $k_{obs}$, $k_{MM}[MeOH]^2$ with hydrogen-bonded methanol as electrophile, and $k_{MAP}[MeOH][AP]$ with hydrogen-bonding disrupted by the aprotic solvent.

K2NbF7로부터 Na 열환원 공정에 의한 니오븀 분말의 제조 (Preparation of Niobium Powders by Sodiothermic Reduction of K2NbF7)

  • 윤재식
    • 한국재료학회지
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    • 제19권7호
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    • pp.386-390
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    • 2009
  • Niobium(Nb) and Tantalum(Ta) are rarely found apart in nature and never in the free state. The element niobium amounts to 3% of the crustal abundance. On the whole, the niobium capacitor showed somewhat more unstable characteristics than the commercial tantalum capacitors, but is nonetheless considered applicable as a future substitute for tantalum capacitors. In this study, niobium powder was made from potassium heptafluoroniobite($K_2NbF_7$) by using sodium(Na) as a reductant and KCl and KF as diluents based on the hunter sodiothermic reduction method.,In order to obtain a high surface area niobium powder via the sodiothermic reduction method, a certain amount of diluent, such as alkali metal halides selected from NaCl, KCl, KF and NaF, was added in the raw materials to be reduced. However, if a higher surface area of powder is required, more diluents need to be used in the said method in order to produce niobium powder. But when more diluents are used, the niobium powder will be contaminated with more impurities and the yield will also decreased.

Reaction of Lithium Gallium Hydride with Selected Organic Compounds Containing Representative Functional Groups

  • 최정훈;윤문영;윤종훈;정동원
    • Bulletin of the Korean Chemical Society
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    • 제16권5호
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    • pp.416-421
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    • 1995
  • The approximate rates and stoichiometry of the reaction of excess lithium gallium hydride with selected organic compounds containing representative functional groups were examined under the standard conditions (diethyl ether, 0 $^{\circ}C)$ in order to compare its reducing characteristics with lithium aluminum hydride and lithium borohydride previously reported, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, and amines evolve hydrogen rapidly and quantitatively. However lithium gallium hydride reacts with only one active hydrogen of primary amine. Aldehydes and ketones of diverse structure are rapidly reduced to the corresponding alcohols. Conjugated aldehyde and ketone such as cinnamaldehyde and methyl vinyl ketone are rapidly reduced to the corresponding saturated alcohols. p-Benzoquinone is mainly reduces to hydroquinone. Caproic acid and benzoic acid liberate hydrogen rapidly and quantitatively, but reduction proceeds slowly. The acid chlorides and esters tested are all rapidly reduced to the corresponding alcohols. Alkyl halides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced slowly. Benzonitrile consumes 2.0 equiv of hydride rapidly, whereas capronitrile is reduced slowly. Nitro compounds consumed 2.9 equiv of hydride, of which 1.9 equiv is for reduction, whereas azobenzene, and azoxybenzene are inert toward this reagent. Cyclohexanone oxime is reduced consuming 2.0 equiv of hydride for reduction at a moderate rate. Pyridine is inert toward this reagent. Disulfides and sulfoxides are reduced slowly, whereas sulfide, sulfone, and sulfonate are inert under these reaction conditions. Sulfonic acid evolves 1 equiv of hydrogen instantly, but reduction is not proceeded.

Synthesis and Characterization of New Intermetallic Compounds $M_3(AsTe_3)_2$ (M=Cr, Fe, Co)

  • 정진승;김현학;강석구;채원식;김돈;이성한
    • Bulletin of the Korean Chemical Society
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    • 제18권10호
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    • pp.1105-1108
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    • 1997
  • The new amorphous intermetallic compounds, M3(AsTe3)2: M=Cr, Co, Fe, were synthesized by the precipitation reaction of the Zintl anion AsTe33- with the divalent transition metal halides in aqueous solution and analyzed by EDS equipped with SEM and PIXE. The empirical formula of the specimens was found to be Fe3.0As1.8Te5.9, Co3.0As2.1Te6.5, and Cr3.0As2.0Te6.9 by the quantitative elemental analysis. The dc specific resistivity of the materials was measured as a function of temperature in the range from 20 to 300 K, in which their resistivity of Cr3(AsTe3)2 was largely dependent on temperature, while those of Co3(AsTe3)2 and Fe3(AsTe3)2 were only slightly dependent on temperature. To characterize the spin glass state of the specimens, the ac and dc magnetic susceptibility were measured and it was found that Co3(AsTe3)2 and Fe3(AsTe3)2 undergo a transition to a spin glass state at 6 K and 38 K, respectively. Magnetization data are reported as both thermal remanent magnetization (TRM) and isothermal remanent magnetization (IRM) as a function of magnetizing field and temperature.

Reduction of Representative Organic Functional Groups with Gallane-Trimethylamine

  • 최정훈;오영주;김민정;황북기;백대진
    • Bulletin of the Korean Chemical Society
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    • 제18권3호
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    • pp.274-280
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    • 1997
  • The rates and stoichiometry of the reaction of gallane-trimethylamine with selected organic compounds containing representative functional groups were examined in tetrahydrofuran solution under standardized conditions (THF, 0 ℃). And its reducing characteristics were compared with those of aluminum hydride-triethylamine(AHTEA). The rate of hydrogen evolution from active hydrogen compounds varied considerably with the nature of the functional group and the structure of the hydrocarbon moiety. Alcohols, phenol, amines, thiols evolved hydrogen rapidly and quantitatively. Aldehydes and ketones were reduced moderately to the corresponding alcohols. Cinnamaldehyde was reduced to cinnamyl alcohol, which means that the conjugated double bond was not attacked by gallane-trimethylamine. Carboxylic acids, esters, and lactones were stable to the reagent under standard conditions. Acid chlorides also were rapidly reduced to the corresponding alcohols. Epoxides and halides were inert to the reagent. Caproamide and nitrile were stable to the reagent, whereas benzamide was rapidly reduced to benzylamine. Nitropropane, nitrobenzene and azoxybenzene were stable to the reagent, whereas azobenzene was reduced to 1,2-diphenylhydrazine. Oximes and pyridine N-oxide were reduced rapidly. Di-n-butyl disulfide and dimethyl sulfoxide were reduced only slowly, but diphenyl disulfide was reduced rapidly. Finally, sulfones and sulfonic acids were inert to the reagent under the reaction.

Au/Ag 이중층 전극 구조를 이용한 페로브스카이트 태양전지 (Au/Ag Bilayer Electrode for Perovskite Solar Cells)

  • 이준영;조성진
    • 한국재료학회지
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    • 제32권1호
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    • pp.51-55
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    • 2022
  • Generally, Au electrodes are the preferred top metal electrodes in most perovskite solar cells (PSCs) because of their appropriate work function for hole transportation and their resistance to metal-halide formation. However, for the commercialization of PSCs, the development of alternative metal electrodes for Au is essential to decrease their fabrication cost. Ag electrodes are considered one of the most suitable alternatives for Au electrodes because they are relatively cheaper and can provide the necessary stability for oxidation. However, Ag electrodes require an aging-induced recovery process and react with halides from perovskite layers. Herein, we propose a bilayer Au/Ag electrode to overcome the limitations of single Au and Ag metal electrodes. The performance of PSCs based on bilayer electrodes is comparable to that of PSCs with Au electrodes. Furthermore, by using the bilayer electrode, we can eliminate the aging process, normally an essential process for Ag electrodes. This study not only demonstrates an effective method to substitute for expensive Au electrodes but also provides a possibility to overcome the limitations of Ag electrodes.

A Study on the Implementation of a Portable Hologram Recording System for Optical Education

  • Cheolyoung, Go;Juyoung, Hong;Kwangpyo, Hong;Eunyeop, Shin;Leehwan, Hwang;Soonchul, Kwon;Seunghyun, Lee
    • International Journal of Advanced Culture Technology
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    • 제10권4호
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    • pp.478-486
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    • 2022
  • Holography is a human-friendly technology that can express 3D stereoscopic information without eye fatigue. You can experience the mysterious features of light directly and indirectly, and you can also experience the principles of 3D imaging, which makes it a very good curriculum. As such, although holography is very effective in teaching students optics and 3D imaging technology, it has not yet been systematically established. The reason is the cost burden such as expensive equipment and laboratories, and the lack of easily accessible educational equipment. We implemented a portable holographic recording system to solve this problem. In addition, since silver halides, which use harmful chemicals, are not used in the process of developing the recording medium, and photopolymers are used, it is possible to educate not only the general public but also young students. In order to improve the completeness of the recorded result, the mechanism part, light source, and recording medium part of the production system were newly constructed to complement all the existing problems. The proposed system will make holography easily accessible to many people in a variety of fields, not just education. Through the interesting experience of various features and principles of light and the production of holograms with high satisfaction, we hope to popularize them in various fields such as education.

Imidoyl Halide의 가수분해 반응메카니즘과 그의 반응속도론적 연구 (Kinetics and Mechanism of the Hydrolysis of Imidoyl Halides)

  • 김태린;김진희;장병두;이광일;김응조
    • 대한화학회지
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    • 제20권1호
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    • pp.48-55
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    • 1976
  • N-(2,4-dinitrophenyl)-benzimidoyl chloride의 여러가지 유도체의 가수분해 속도상수를 측정하여 넓은 pH 범위에서 잘 맞는 반응속도식을 구하였다. 이 식에 의하면 아직 잘 알려져 있지 않은 산성과 염기성 용액속에서 가수분해 반응메카니즘을 정량적으로 잘 설명할 수 있었다. 즉 pH 7.0 이하에서는 carbonium ion 중간체를 거쳐 반응이 진행되는 $S_n1$ 반응과정이며, pH 8.5 이상에서는 hydroxide ion과 imidoyl chloride 농도에 비례하는 $S_n2$ 반응메카니즘에 의해 가수분해가 진행되며, pH 7.0∼8.5 사이에서는 이 두 반응이 경쟁적으로 일어남을 알았다.

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