• Title/Summary/Keyword: Carbon-carbon bond formation

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Photocyclization Reactions of N-(Trimethylsilylmethoxyalkyl)Phthalimides. Efficient and Regioselective Route to Heterocycles

  • Yoon Ung Chan;Oh Ju Hee;Lee, Sang Jin;Kim, Dong Uk;Lee, Jong Gun;Kang Kyung-Tae;Mariano Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.13 no.2
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    • pp.166-172
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    • 1992
  • Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethoxyalkyl)phthalimides(alkyl=E thyl, n-propyl, n-butyl, n-pentyl, and n-octyl). Photocyclizations occur in methanol in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from oxygen in the $\alpha-silylmethoxy$ groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate $\alpha-silylmethoxy$ cation radicals and cyclization by radical coupling are proposed. In contrast, photoreaction of N-(trimethylsilylmethoxyethyl) phthalimide in acetone follows different reaction routes to produce two cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon $\alpha$ to silicon and oxygen atoms via triplet carbonyl hydrogen abstraction triplet carbonyl silyl group abstraction pathways. The normal singlet SET pathway dominates these triplet processes for photoreaction of this substance in methanol. The efficient and regioselective cyclization reactions observed for photolysis in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

Deintercalation and Thermal Stability of Na-graphite Intercalation Compounds

  • Oh, Won-Chun
    • Carbon letters
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    • v.2 no.1
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    • pp.22-26
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    • 2001
  • Na alloyed graphite intercalation compounds with stage 1 and 2 were synthesized using the high temperature and pressure technique. Thermal stability and staging transitions of the compounds were investigated depending on heating rates. The thermal stability and temperature dependence of the deintercalation compounds were characterized using differential scanning calorimeter (DSC) analyzer. Enthalpy of formations were confirmed at temperatures between 25 and $500^{\circ}C$, depending on the various heating rates. The structure ions and interlayer spaces of the graphite were identified by X-ray diffraction (XRD). Diffractograms of stages with non-integral (00l) values were obtained in the thermal decomposition process, and stacking disorder defects and random stage modes were observed. The average value of the interlayer C-C bond lengths were found approximately $2.12{\AA}$ and $1.23{\AA}$ from the diffractions. Based on the stage transition, the degree of the deintercalaton has a inverse-linear relationship against the heating rate.

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Substituent Effects on the Leaving Groups in Benzyl Arenesulfonates (Benzyl Arenesulfonate의 離脫基의 置換基效果에 關한 硏究 (第 1 報))

  • Yoh Soo Dong
    • Journal of the Korean Chemical Society
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    • v.19 no.2
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    • pp.116-122
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    • 1975
  • Determination has been made of the kinetics of the reaction of benzyl arenesulfonates with pyridine in acetone. The substituent effects of the leaving groups in benzyl arenesulfonates are correlated by Hammett equations, with the exception of p-MeO and $p-NO_2$ groups, where the electron attracting substituents in the benzyl arenesulfonate increase the rate. The substituent effects of the leaving groups are as expected due to the nucleophilic attack of amine on the benzyl carbon atom. This can be understood in terms of changes in bond formation (C-N) and bond breaking (C-O) in the transition state with charges in electron-attracting ability of the substituents. The predicted substituent effects may indicate a small increase in bond formation and thus a tighter transition state, in benzyl p-bromobenzene sulfonate than in benzyl p-nitrobenzenesulfonate. Predicting made by Thornton concerning the substituent effects on $S_N2$ transition state structures agrees with the changes in bond formation and bond breaking.

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Hydrogen Bonding-Driven Assembling of Thin Multiwalled Carbon Nanotubes (수소결합에 의한 얇은 다중벽 탄소나노튜브의 자기조립)

  • Han, Joong-Tark;Kim, Sun-Young;Woo, Jong-Seok;Lee, Gun-Woong
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2007.11a
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    • pp.426-427
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    • 2007
  • Here we describe the formation of a self-assembled film of thin multiwalled carbon Nanotubes(t-MWNT) modified with hydroxy groups through hydrogen peroxide treatment. Morphologies of t-MWNT films could be controlled by the various coating method, such as filtering, drop casting, spraying method, etc. The results show that on densification of the CNT suspension during drying, multiple hydroxy group-modified MWNTs can be self-assembled through strong surface hydrogen bond interaction while MWNTs usually exist an entangled state in the film. The interaction between t-MWNT was illustrated from Raman spectrum of spray coated films.

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The Charge Transfer Complexes of Monoalkylbenzene with Iodine in Carbon Tetrachloride (I)

  • Oh-Cheun Kwun
    • Bulletin of the Korean Chemical Society
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    • v.1 no.2
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    • pp.62-68
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    • 1980
  • Ultraviolet spectrophotometric investigations have been carried out the systems of monoalkylbenzene with iodine in carbon tetrachloride. The results reveal the formation of one to one molecular complexes. The equilibrium constants for these complexes of representative monosubstituted benzene reveal the following order of increasing stability: benzene < methyl- < ethyl- < n-propyl-benzene. The value of ${\Delta}H$, ${\Delta}G$, and ${\Delta}S$ for interaction of a number of monoalkyl substituted benzene with iodine has been determinated. In general, as ΛH becomes increasingly negative, corresponding decreases in ${\Delta}G$ and ${\Delta}S$ values are observed, and these variation are linear. The thermodynamic constants become increasingly negative with increasing monoalkyl substitution of the aromatic donor nucleus. The complex bond is therefore weak, and its formation is accompanied by relatively small entropy changes.

Mercury Ions Mediated Phosphorus Containing Carbon Dots as Fluorescent Probe for Biothiols Screening

  • Du, Han;Xu, Hu;Zhao, Yun;Li, Dan;Wang, Yuhong
    • Nano
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    • v.13 no.10
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    • pp.1850116.1-1850116.14
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    • 2018
  • In this study, we report the mercury ions ($Hg^{2+}$) mediated phosphorus-containing carbon dots (PCDs) as a selective "off-on" fluorescence probe for glutathione (GSH), cysteine (Cys) and homocysteine (Hcys). PCDs obtained by hydrothermal reaction are sensitive to $Hg^{2+}$ ions and its fluorescence can be significantly quenched owing to the electron transfer from the lowest unoccupied molecular orbital (LUMO) of PCDs to $Hg^{2+}$. Interestingly, the weak fluorescence of $Hg^{2+}$-mediated PCDs could be gradually recovered with the addition of GSH, Cys and Hcys. This can be attributed to the formation of $Hg^{2+}-S$ complex due to the super affinity of $Hg^{2+}$-sulfydryl bond. The formation of $Hg^{2+}-S$ complex extremely reduces the oxidation ability of $Hg^{2+}$ that inhibits the electron transfer from LUMO of PCDs to $Hg^{2+}$ and re-opens the native electron transition from LUMO to the highest occupied molecular orbital (HOMO) of PCDs. Thus, the green fluorescence of PCDs is switched on. Furthermore, the present $Hg^{2+}$-mediated PCDs assay exhibits a high selectivity for GSH, Cys and Hcy and has been successfully used to detect the total biothiols content in human urine samples.

Corrosion Mechanism and Bond-Strength Study on Galvanized Steel in Concrete Environment

  • Kouril, M.;Pokorny, P.;Stoulil, J.
    • Corrosion Science and Technology
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    • v.16 no.2
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    • pp.69-75
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    • 2017
  • Zinc coating on carbon steels give the higher corrosion resistance in chloride containing environments and in carbonated concrete. However, hydrogen evolution accompanies the corrosion of zinc in the initial activity in fresh concrete, which can lead to the formation of a porous structure at the reinforcement -concrete interface, which can potentially reduce the bond-strength of the reinforcement with concrete. The present study examines the mechanism of the corrosion of hot-dip galvanized steel in detail, as in the model pore solutions and real concrete. Calcium ion plays an important role in the corrosion mechanism, as it prevents the formation of passive layers on zinc at an elevated alkalinity. The corrosion rate of galvanized steel decreases in accordance with the exposure time; however, the reason for this is not the zinc transition into passivity, but the consumption of the less corrosion-resistant phases of hot-dip galvanizing in the concrete environment. The results on the electrochemical tests have been confirmed by the bond-strength test for the reinforcement of concrete and by evaluating the porosity of the cement adjacent to the reinforcement.

Effect of Oxidation Multi-Walled Carbon Nanotubes for Methane Hydrate Formation (산화탄소나노튜브를 이용한 메탄 하이드레이트 형성)

  • Park, Sung-Seek;Kim, Nam-Jin
    • Journal of the Korean Solar Energy Society
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    • v.30 no.5
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    • pp.11-16
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    • 2010
  • Methane hydrate is crystalline ice-like compounds which formed methane gas enters within water molecules composed cavity and each other from physically-bond at specially temperature and pressure condition. $1m^3$ of methane hydrate can be decomposed into the maximum of $216m^3$ of methane gas under standard condition. If these characteristics of hydrate are utilized in the opposite sense, natural gas can be fixed into water in the form of a hydrate solid. Therefore the use of hydrate is considered to be a great way to transport and store natural gas in large quantity. However, when methane hydrate is formed artificially, the amount of gas that is consumed is relatively low, due to the slow reaction rate between water and methane gas. Therefore for practical purposes in the application, the present investigation focuses on increasing the amount of gas consumed by adding chemically oxidized OMWCNTs to pure water. The results show that when 0.003 wt% of oxidation multi-walled carbon nanotubes was added to pure water, the amount of gas consumed was almost four times more than that of pure water indicating its effect in hydrate formation and the hydrate formation time decreased at alow subcooling temperature.

Recent advance on the borylation of carbon-oxygen bonds in aromatic compounds

  • Jeon, Seungwon;Lee, Eunsung
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.4 no.1
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    • pp.16-21
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    • 2018
  • Organoboron compounds and their derivatives are synthetically versatile building blocks because they are readily available, stable, and highly useful for potential organic transformations. Arylboronic esters are of particular interest due to their well-established synthetic methods: transition metal catalyzed borylations of aryl halides. However, the use of aryl halides as an electrophile has one serious disadvantage: formation of toxic halogenated byproducts. A promising alternative substrate to aryl halides would be phenol derivatives such as aryl ethers, esters, carbamates and sulfonates. The phenol derivatives involve several advantages: their abundance, relatively low toxicity and versatile synthetic application. However, utilization of the aryl methyl ether, which is one of the simplest phenol derivatives, remains as a challenge, as C-OMe bond activation requires high activation energy and methoxides are not good leaving groups. Nevertheless, there have been a significant recent progress on ipso-borylation of aryl methyl ether including Martin's nickel catalysis. Here, we review the current advance on the borylation of carbon-oxygen bonds of unactivated C-OMe bond in aromatic compounds.

Effect of $ZnCl_2$ on Formation of Carbonized Phenol Resin Anode

  • Kim Han-Joo;Hong Ji-sook;Son Won-Ken;Park Soo-Gil;Oyama Noboru
    • Journal of the Korean Electrochemical Society
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    • v.3 no.2
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    • pp.85-89
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    • 2000
  • For replacing Li metal at Lithium ion Battery(LIB) system, we used carbon powder material which prepared by Pyrolysis of Phenol resin as starting material. It became amorphous carbon by Pyrolysis through it's self condensation by thermal treatment. Amorphous carbon can be doped with Li intercalation and deintercalation because it has wide interlayer. However, it has a problem with structural destroy due to weak carbon-carbon bond. So, we used $ZnCl_2$ as the pore-forming agent. This inorganic salt was used together with the resin serves not only as the pore-forming agent to form open pores, which grow into a three-dimensional network structure in the cured material, but also as the microstructure-controlling agent to form a loose structure doped with bulky dopants. We used SEM in order to find to difference of structure, and can calculate the distance of interlayer by XRD analysis. CV test showed oxidation and reduction.