• Title/Summary/Keyword: Carbonyl reduction

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Mild and Efficient Reduction of α,β-Unsaturated Carbonyl Compounds, α-Diketones and Acyloins with Sodium Borohydride/Dowex1-x8 System

  • Zeynizadeh, Behzad;Shirini, Farhad
    • Bulletin of the Korean Chemical Society
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    • v.24 no.3
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    • pp.295-298
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    • 2003
  • α,β-Unsaturated aldehydes and ketones are regioselectively reduced to the corresponding allylic alcohols with /Dowex1-x8 system in THF at room temperature. This system is also efficient for the conversion of α-diketones and acyloins to the vicinal diols in refluxing THF.

Effect of an Extra Chloro Substituent on Photochemistry of o-Alkylphenacyl Chloride

  • Park, Bong-Ser;Jeong, Seong-Jin
    • Bulletin of the Korean Chemical Society
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    • v.30 no.12
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    • pp.3053-3056
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    • 2009
  • The title compound, ${\alpha},{\alpha}$-dichloro-o-methylacetophenone, was prepared and its photochemical behavior was investigated. Addition of an extra chlorine at alpha position to the carbonyl showed many different features from photochemical reactivities of mono chloro analogue, 2,5-dimethylphenacyl chloride. In benzene, a rearrangement product with a formal 1,5-Cl shift and a reduction product were formed beside indanone. In methanol, solvolysis and cyclization of a common dienol intermediate occurred at comparable reaction rates.

Enhancement of Fluorescent Properties and Electrochemical Reduction of Coumarin Derivatives (Coumarin 유도체들의 전기화학적 환원과 형광성의 증강)

  • Chun, Hyun Ja;Kim, Sung Hyun;Jung, Eun Joo;Lee, Hye Suk;Kim, Il Kwang
    • Analytical Science and Technology
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    • v.18 no.1
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    • pp.89-95
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    • 2005
  • Studies on the electrochemical reduction of 7-acetoxy-4-bromomethyl-coumarin (ABMC), 7-acetoxymethyl coumarin (AMC), and coumarin in 0.1 M tetraethyl ammonium perchlorate acetonitrile solution were carried out with direct current, differential pulse polarography, cyclic voltammetry, and controlled potential coulometry. The electrochemical reduction of ABMC was proceeded through three irreversible steps coupled with the chemical reactions. The solution color was changed to yellow when the carbonyl group was reduced during second step and the color change was independent with bromo group of ABMC. Fluorescent intensity was highest when the electrochemical reduction was controlled at near the overpotential of supporting electrolyte (-2.3 volts).

Comparison of recovery rates of DNPH-Cartridge sampler in the analysis of odorous carbonyl compounds (DNPH Cartridge를 이용한 악취성 카르보닐화합물의 분석회수율 비교)

  • Hong, One-Feel;Lim, Sung-Min;Kim, Ki-Hyun
    • Analytical Science and Technology
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    • v.23 no.5
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    • pp.446-456
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    • 2010
  • In this study, the performance characteristics of DNPH sampling were investigated in the collection and analysis of 5 carbonyl compounds (CC) in air using the cartridge products produced by three different makers. For these experiments, gaseous standards of 5 CCs were prepared to cover 9 concentration levels for each compound (33~2600 nmol). Some cartridge products exhibited relatively high blank values of acetaldehyde (AA) and propionaldehyde (PA). The recovery rates of all three cartridges showed moderate reduction as the molecular weight of CC increased. In addition, when the recovery rate was compared by percent error (%), the most stable patterns were achieved in the intermediate concentration range of 263~1312 nmol (in case of AA). The overall results of our study suggest that the optimal range of recovery for a given concentration range should be considered to obtain the most reliable data for the DNPH cartridge method.

Characterization of the UV Oxidation of Raw Natural Rubber Thin Film Using Image and FT-IR Analysis

  • Kim, Ik-Sik;Lee, Bok-Won;Sohn, Kyung-Suk;Yoon, Joohoe;Lee, Jung-Hun
    • Elastomers and Composites
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    • v.51 no.1
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    • pp.1-9
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    • 2016
  • Characterization of the UV oxidation for raw natural rubber (NR) was investigated in controlled conditions through image and FT-IR analysis. The UV oxidation was performed on a thin film of natural rubber coated on a KBr window at 254 nm and room temperature to exclude the thermal oxidation. Before or after exposure to UV light, image of the NR thin film was observed at a right or tilted angle. FT-IR absorption spectra were measured in transmission mode with the UV irradiation time. The UV oxidation of NR was examined by the changes of absorption peaks at 3425, 1717, 1084, 1477, 1377, and $833cm^{-1}$ which were assigned to hydroxyl group (-OH), carbonyl group (-C=O), carbon-oxygen bond (-C-O), methylene group $(-CH_2-)$, methyl group $(-CH_3)$, and cis-methine group $(cis-CCH_3=CH-)$, respectively. During the initial exposure period, the results indicated that the appearance of carbonyl group was directly related to the reduction of cis-methine group containing carbon-carbon double bond (-C=C-). Most of aldehydes or ketones from carbon-carbon double bonds were formed very fast by chain scission. A lot of long wide cracks with one orientation at regular intervals which resulted in consecutive chain scission were observed by image analysis. During all exposure periods, on the other hand, it was considered that the continuous increment of hydroxyl and carbonyl group was closely related to the decrement of methylene and methyl group in the allylic position. Therefore, two possible mechanisms for the UV oxidation of NR were suggested.

Enhanced Electrochemifluorescence and Reduction Mechanism of Acetoxy Coumarin Derivatives in Acetonitrile Solution

  • Kim, Sung-Hyun;Jung, Eun-Joo;So, Eun-Mi;Shen, Chang-Zhe;Chun, Hyun-Ja;Kim, Young-Man;Kim, Il-Kwang
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1329-1334
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    • 2006
  • The electrochemical reduction of coumarin, 7-acetoxy-4-methyl coumarin (AMC), and 7-acetoxy-4-bromomethyl coumarin (ABMC), in 0.1 M tetraethyl ammonium perchlorate/acetonitrile solution was carried out by direct current, differential pulse polarography, cyclic voltammetry, and controlled potential coulometry. The electrochemical reduction of ABMC was proceeded through three steps of electron transfer coupled with the chemical reactions. The color of solution was changed to yellow when the carbonyl group was reduced during 2nd step (-1.8 volts) and independented with cleavage of bromo group. Highest fluorescence intensity showed when the electrochemical reduction of AMC was controlled at near the potential (-2.3 volts vs. Ag/AgCl).

Selective Reduction of Keto Esters with Zinc Borohydride (수소화붕소 아연에 의한 케토에스데르의 선택환원)

  • Nung Min Yoon;Jahyo Kang
    • Journal of the Korean Chemical Society
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    • v.19 no.5
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    • pp.360-366
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    • 1975
  • Selective reduction of carbonyl group with zinc borohydride in the presence of ester functional group was demonstrated with seven representative keto esters. Either hydroxy esters or lactones were obtained in good yields; ethyl 6-hydroxyheptanoate ($83.0{\%}$), ethyl 2,6-dimethyl-4-hydroxy-2-cyclohexenecarboxylate ($82.3{\%}$), ethyl p-(${\alpha}$-hydroxyethyl)-phenylacetate ($78.9 {\%}$), 4-phenylbutyrolactone ($70.2{\%}$), and 3-phenylphthalide ($92.4{\%}$) were obtained from the corresponding keto esters.

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Reaction of Lithium Cyanoaluminum Hydride with Selected Organic Compounds Containing Representative Functional Groups. Comparison of Reducing Characteristics between Lithium and Sodium Cyanoaluminum Hydrides

  • Cha, Jin-Soon;Yu, Se-Jin
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1588-1592
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    • 2009
  • Lithium cyanoaluminum hydride (LCAH) was prepared by the metal cation exchange reaction of sodium cyanoaluminum hydride with lithium chloride in tetrahydrofuran. The reducing characteristics of LCAH were explored systematically by the reaction with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 0 ${^{\circ}C}$). The reducing ability of LCAH was also compared with of the sodium derivative, sodium cyanoaluminum hydride (SCAH). Generally, the reducing behavior of LCAH resembles that of SCAH closely, but the reactivity of LCAH toward representative organic functional groups appeared to be stronger than that of SCAH. Thus, the regent reduces carbonyl compounds, epoxides, amides, nitriles, disulfides, carboxylic acids and their acyl derivatives to the corresponding alcohols or amines, at a relatively faster rate than that of SCAH. The cyano substitution, a strong election-withdrawing group, diminishes the reducing power of the parent metal aluminum hydrides and hence effects the alteration of their reducing characteristics.

Reduction of Selected Carbonyl Compounds with 8-Oxyquinoline Dihydroboronite. Selective Reduction of Aldehydes in the Presence of Ketones

  • Kim, Sung-Gak;Yang, Sung-Bong;Kang, Ho-Jung
    • Bulletin of the Korean Chemical Society
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    • v.5 no.6
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    • pp.240-244
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    • 1984
  • 8-Oxyquinoline dihydroboronite is prepared by mixing equimolar amounts of 8-hydroxyquinoline and borane-dimethyl sulfide complex in tetrahydrofuran at room temperature and its structure is determined by spectroscopic methods. The reagent is shown to be an extremely mild reducing agent and reduces aldehydes, cyclohexanones, and acid chlorides to some extent. The reagent in the presence of 0.1 equiv of boron trifluoride etherate in tetrahydrofuran at room temperature reduces selectively aldehydes in the presence of ketones, while the reagent in the presence of 1 equiv of boron trifluoride etherate rapidly reduces simple aldehydes and ketones but does not reduce carboxylic acids, esters, and amides.

Preparation of Copper Nanoparticles in Cellulose Acetate Polymer and the Reaction Chemistry of Copper Complexes in the Polymer

  • Shim, Il-Wun;Noh, Won-Tae;Kwon, Ji-Woon;Jo, Jung-Young;Kim, Kyung-Soo;Kang, Dong-Hee
    • Bulletin of the Korean Chemical Society
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    • v.23 no.4
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    • pp.563-566
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    • 2002
  • Copper complexes have been directly incorporated into cellulose acetate (CA) and the resulting light blue colored homogeneous films of 5-20 wt.% copper acetate complex concentrations are found to be thermally stable up to 200 $^{\circ}C$. The reaction chem istry of Cu in CA has been investigated by reacting them with small gas molecules such as CO, H2, D2, O2, NO, and olefins in the temperature range of 25-160 $^{\circ}C$, and various Cu-hydride, -carbonyl, -nitrosyl, and olefin species coordinated to Cu sites in CA are characterized by IR and UV/Vis spectroscopic study. The reduction of Cu(II) complexes by reacting with H2 gas at the described conditions results in the formation of Cu2O and copper metal nanoparticles in CA, and their sizes in 30-120 nm range are found to be controlled by adjusting metal complex concentration in CA and/or the reduction reaction conditions. These small copper metal particles show various catalytic reactivity in hydrogenation of olefins and CH3CN; CO oxidation; and NO reduction reactions under relatively mild conditions.