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

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Photoinduced Chemical Linking of Difluoride Molecules with Graphene

  • Yang, Mi-Hyeon;Lee, Gyeong-Jae;Kumar, Yogesh;Im, Gyu-Uk;An, Jong-Ryeol
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.198.1-198.1
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    • 2014
  • Many efforts have been devoted on chemical modification of graphene layer to modulate its electrical properties. In the previous report, laser irradiation on the CYTOP(perfluoropolymer) doped graphene layer induces chemical modification of it, resulting in the insulating I-V characteristics. While the results strongly denoted C-F bond formation after irradiation, the detailed process of photo-induced chemical change is not known yet. To probe this, we utilized synchrotron based SPEM (scanning photoelectron emission spectroscopy) in NSRRC, Taiwan. We irradiate the sample by photon of 614 eV in a stepwise manner as a function of time. As photon irradiation increased, difluoride moieties in the CYTOP was broken, and then formed mono-fluoride with carbon atoms consisting graphene layer.

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Ring-Opening Reaction of 2,2-gem-Diphenylaziridine (2,2-gem-Diphenylaziridine의 開環反應)

  • Hahn, Chi-Sun;Nam-Goong, Ha-Il;Kang, Yong-Ik
    • Journal of the Korean Chemical Society
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    • v.13 no.3
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    • pp.229-232
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    • 1969
  • A study of the ring-opening reaction of 2,2-gem-diphenylaziridine by treating with acetic acid has been undertaken. The structure of the ring-opened product was confirmed as 1,1-diphenyl-2-aminoethyl acetate. It is most likely that the reaction proceeds through the cleavage of a bond between nitrogen and tertiary carbon atoms in the aziridine ring, followed by the formation of a carbonium ion intermediate.

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S$_H$2 Reaction on Silicon-Carbon Bond in the Photoreactions of 2, 3-Benzo-1, 1-diphenyl(or dimethyl)-1-sila-2-cyclobutene with Carbonyl Compounds

  • Kang, Kyung-Tai;Okazaki, Renji;Inamoto, Naoki
    • Bulletin of the Korean Chemical Society
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    • v.5 no.1
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    • pp.32-37
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    • 1984
  • The photoreaction of 2, 3-benzo-1, 1-diphenyl (or dimethyl)-1-sila-2-cyclobutene (9 or 10) with an aldehyde or ketone results in 1:1 cycloadduct of [4 + 2] type. In the reactions of 2, 3-benzo-1, 1-dimethyl-1-sila-2-cyclobutene (10) with acetone and butanone, another 1:1 adducts (13) were also formed, respectively. The following facts indicate that the formation of adduct involves an attack of a triplet carbonyl compound on the silicon of the benzosilacyclobutene, an $S_H2$ process. (1) Even when the reaction of 9 with acetophenone was carried out under conditions such that more than 99% of incident light was absorbed only by acetophenone using the filter solution of aq. cupric sulfate, the same adduct was still formed. (2) When the reaction of 9 with acetone was carried out under oxygen atmosphere, only trace amount of adduct was formed.

Near IR Spectroscopic Studies on the Interaction between Acetamide and Lu$(dpm)_3$ in Carbon Tetrachloride

  • 최영상;김홍순;유정아;이상원;박정희;윤창주
    • Bulletin of the Korean Chemical Society
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    • v.17 no.6
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    • pp.511-514
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    • 1996
  • The interactions between Ln(dpm)3 [Ln3+=Eu3+, Yb3+, Pr3+, Sm3+, Tb3+and Ho3+; dpm=tris 2,2,6,6-tetramethylheptane-3,5-dionate] and acetamide in CCl4 solution were investigated using near IR absorption spectroscopy. From the measured 2 νC=O+ amide Ⅲ combination band of acetamide in the region of 2130-2180 nm(4695-4587 cm-1), it was found that acetamide is coordinating through its carbonyl oxygen atom to Ln(dpm)3[C=O…Ln(dpm)3)] and forms only 1 : 1 stoichiometric Ln(dpm)3- acetamide complex. The ΔHo values for the formation of Ln(dpm)3-acetamide obtained from the temperature studies are -39.1, -28.4, -25.5, -24.7, -21.1 and -17.7 kJ mol-1 for Eu(dpm)3, Yb(dpm)3, Pr(dpm)3, Sm(dpm)3, Tb(dpm)3 and Ho(dpm)3, respectively, which are larger than those of the hydrogen bond between amide and various hydrogen acceptors. Except Eu(dpm)3 and Yb(dpm)3, -ΔHovalue increases as the ionic size increases.

The Versatile Conversion of Acyclic Amides to a-Alkylated Amines

  • Suh, Young-Ger;Lee, Do-Sang;Shin, Dong-Yun;Jung, Jae-Kyung;Kim, Seok-Ho
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.350.2-350.2
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    • 2002
  • The reaction of N-acyliminium ion with a variety of nucleophiles is one of the powerful method to introduce various substituents at the a-carbon of an amine. Particularly this type of inter and intramolecular C-C bond formation can be effectively applied to the synthesis of the bioactive natural or unnatural compounds as well as many bioactive peptidomimetics. Accordingly. much attention has been devoted to the practical and efficient methods for the generation of acyliminium ion precursors though there are many important aspects in the reaction involving N-acyliminium ions. (omitted)

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Mechanical Properties of DLC Films and Duplex Plasma Nitriding/DLC Coating Treatment Process (DLC 박막과 복합처리(Nitriding/DLC)한 박막의 기계적 특성 비교)

  • Park, Hyun-Jun;Kim, Min-Chae;Kim, Sang-Sub;Moon, Kyoung-Il
    • Journal of the Korean institute of surface engineering
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    • v.53 no.6
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    • pp.306-311
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    • 2020
  • In this work, diamond-like carbon (DLC) films are coated onto plasma nitrided AISI 4140 steel by DC-pulsed PECVD. One problem of DLC films is their very poor adhesion on steel substrates. The purpose of the nitriding was to enhance adhesion between the substrate and the DLC films. The white layer formation is avoided. Plasma nitriding increased adhesion from 8 N for DLC coating to 25 N for duplex coating. Duplex plasma nitriding/DLC coating was proven to be more effective in improving the adhesion. The purpose of the bond layer was to enhance adhesion between the substrate and the DLC films.

Synthesis and E-Beam-Mediated Gas Phase Fragmentation of Thiol-Containing Furoxans for Nanopatterned Alkyne Formation on Gold Surface

  • Koo, Hyun-Seo;Park, Kyung-Moon;Hwang, Kwang-Jin
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3583-3587
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    • 2010
  • Furoxanthiols PFT and BPFT possessing thiomethyl or thiobenzyl groups in the furoxan ring were designed and synthesized as potential light-sensitive alkyne precursors on a gold surface. The synthesis of thiofuroxans PFT and BPFT was performed from the corresponding halofuroxans 1b and 2c, respectively, by the substitution with potassium thioacetate in ethyl acetate/ethanol or DMF, followed by basic hydrolysis as the key reactions. Electron-beammediated fragmentation of furoxans 1c and 2d in a mass spectrometer afforded the corresponding aryl alkyne fragments, with the evolution of NO in high preference. In the cases of thiofuroxans PFT and BPFT, carbon-sulfur bond cleavage was observed as a representative fragmentation, producing M-SH and M-SAc peaks, which competed with the release of NO. In the fragmentation of mono-aryl furoxan 1c, the release of molecule of NO was predominately observed to produce an M-NO fragment as a base peak by the formation of trimembered thiiranium or azirine intermediate.

Studies on the Quaternization of Tertiary Amines (Ⅱ). Kinetics and Mechanism for the Reaction of Substituted Phenacyl Bromides with Substituted Pyridines (3차 아민의 4차화반응에 관한 연구 (제2보). 치환 브롬화페나실류와 치환 피리딘류와의 반응에 관한 반응속도론적 연구)

  • Yoh Soo Dong;Kwang Taik Shim;Lee Kyung A
    • Journal of the Korean Chemical Society
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    • v.25 no.2
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    • pp.110-118
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    • 1981
  • Kinetics and mechanism for the reaction of substituted phenacyl bromides with substituted pyridines have been determined at 25, 35 and $45^{\circ}C$ in methanol and dimethylformamide by the conductivity method. The rate constants for the reaction of various pyridines with phenacyl bromide shown that electron-donating substituents in the pyridine increase the rate, while electron-attracting one decrease in both solvents. The effect of substituents in substrate, the rate being increased by electron-attracting substituents. This is as expected for nucleophilic attack of amines on the carbon atom. Isokinetic and $Br{\psi}nsted$ linear relationship were shown in the reaction of phenacyl bromide with pyridines in both solvent in which isokinetic temperature were obtained 614, $202^{\circ}K$ and ${\beta}$ values were 0.29, 0.36 in methanol and dimethylformamide respectively. In the case of the reaction of substituted phenacyl bromide with pyridines, isokinetic temperature decreases with increasing electron-attracting ability of the substituents in the phenacyl bromide, while the ${\beta}$ values were reverse. From the above results, it can be inferred that N…C bond formation decreases progressively from p-chloro- to p-methoxyphenacyl bromide and the bond formation predominates in DMF than methanol. The ${\rho}$ values of Hammett equation of the reaction of phenacyl bromide with substituted pyridines are negative in both solvent, but its value was larger negative in DMF than methanol and the ${\rho}$ value of that of substitutted substrates with pyridine was 0.3, the low value is ascribed to direct $S_N2$ attack of the nitrogen atom in pyridine ring at the methylene carbon.

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Nucleophilic Substitution at a Carbonyl Carbon Atom (IX). Solvolysis of 2-Furoyl Chloride and 2-Thenoyl Chloride in Binary Mixtures (카르보닐탄소원자의 친핵성 치환반응 (제9보). 이성분 혼합용매에서 2-염화테노일 및 2-염화퓨로일의 가용매분해반응)

  • Son Jin-Eon;Sang-Kee Yoon;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.23 no.6
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    • pp.339-348
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    • 1979
  • The kinetics of the solvolysis of 2-furoyl chloride and 2-thenoyl chloride in $MeOH-H_2O,\;EtOH-H_2O,\;(Me)_2CO-H_2O,\;MeCN-H_2O$ and MeCN-MeOH has been investigated. The rates were faster in protic solvents than in aprotic solvents. This was caused by the bond breaking of leaving group through hydrogen-bonding solvation of protic solvents. In MeCN-M$\'{e}$OH the rate in MeOH rich solvents was faster than in MeCN rich solvents by the specific solvation of alcoholic hydrogen and there was a maximum rate of reaction at MeOH mole fraction of 0.8. The reaction rates of solvolysis were considerably slower than those of benzoyl chloride owing to the electron withdrawing effect of thienyl and furyl groups. It was concluded that solvolytic reaction proceeds via a dissociative $S_N2$ mechanism in which bond-breaking precedes bond-formation at the transition state.

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Liquid Phase Hydrogenation of Croton Aldehyde with Nickel Catalysts (니켈촉매에 의한 크로톤 알데히드의 액상 수소첨가반응)

  • Lee, Hak Sung;Park, Young Hae;Kim, Yong Sup
    • Applied Chemistry for Engineering
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    • v.5 no.3
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    • pp.509-516
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    • 1994
  • Liquid phase hydrogenation come into use for the removal process of unsaturated hydrocarbon such as croton aldehyde. The croton aldehyde is generated in a very small amount as by-product in the ethanol production, and it is converted into n-butanol through hydrogenation. Liquid phase hydrogenation is low energy consumption process as compared with gas phase hydrogenation. The nickel catalyst is selected with respect to the economic aspect such as durability and cost. The analysis of the conversion were performed by method of the PMT(permangante time) test. The PMT was sharply decreased as the initial concentrations of croton aldehyde in the ethanol solution were increased. The hydrogenation of croton aldehyde to n-butanol was carried out in sequence after the saturation of the carbon-carbon double bond. The formation of both butyraldehyde and n-butanol followed zero order kinetics. Within expermental conditions the PMT gets longer as reaction temperature goes higer and as LHSV becomes slower, while the reaction pressure has almost no relation with PMT.

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