• Title/Summary/Keyword: Benzyl alcohol oxidation

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Oxidation of Benzyl Alcohols with Extraordinarily High Kinetic Isotope Effects

  • Jo, Myeong-Ran;Seok, Won-K.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.3003-3008
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    • 2011
  • Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.

Preparation of Ag/TiO2 Particle for Aerobic Benzyl Alcohol Oxidation (Aerobic Benzyl Alcohol Oxidation 반응용 Ag/TiO2 제조)

  • Kim, Chang-Soo;Yoo, Kye Sang
    • Applied Chemistry for Engineering
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    • v.24 no.6
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    • pp.663-667
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    • 2013
  • $Ag/TiO_2$ particle was prepared using various ionic liquids by wet impregnation. The properties of the particles were significantly affected by the composition of ionic liquids. This is mainly attributed to different abilities of an ionic liquid to coordinate with the silver particle, leading to various coagulation of silver particles. The catalytic activity of the prepared samples was examined for the aerobic benzyl alcohol oxidation. Among the particles, $Ag/TiO_2$ prepared with 1-octyl-3-methylimidazolium tetrafluoroborate showed the best catalytic performance.

Benzyl Alcohol Oxidation over H5PMo10V2O40 Catalyst Chemically Immobilized on Sulfur-containing Mesoporous Carbon (황이 포함된 중형기공성 탄소에 화학적으로 고정화된 H5PMo10V2O40 촉매 상에서 Benzyl Alcohol 산화반응)

  • Gim, Min Yeong;Kang, Tae Hun;Choi, Jung Ho;Song, In Kyu
    • Korean Chemical Engineering Research
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    • v.54 no.3
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    • pp.419-424
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    • 2016
  • $H_5PMo_{10}V_2O_{40}$ ($PMo_{10}V_2$) catalyst chemically immobilized on sulfur-containing mesoporous carbon (S-MC) was prepared, and it was applied to the benzyl alcohol oxidation reaction. S-MC was synthesized by a templating method using SBA-15 and p-toluenesulfonic acid as a templating agent and a carbon precursor, respectively. S-MC was then modified to have a positive charge, and thus, to provide sites for the immobilization of $PMo_{10}V_2$. By taking advantage of the overall negative charge of $[PMo_{10}V_2O4_{40}]^{5-}$, $PMo_{10}V_2$ catalyst was immobilized on the S-MC support as a charge matching component. It was revealed that $PMo_{10}V_2$ species were finely and molecularly dispersed on the S-MC via chemical immobilization. In the vapor-phase oxidation of benzyl alcohol, $PMo_{10}V_2$/S-MC catalyst showed higher conversion of benzyl alcohol and higher yield for benzaldehyde and benzoic acid than unsupported $PMo_{10}V_2$ catalyst. The enhanced catalytic performance of $PMo_{10}V_2$/S-MC was due to fine dispersion of $PMo_{10}V_2$ species on the S-MC via chemical immobilization.

Electrochemical Synthesis of 𝛽-Hydroxynitrile by addition of Acetonitrile into Benzyl Alcohol (벤질알코올과 아세토나이트릴의 반응을 통한 𝛽-hydroxynitrile의 전기화학적 합성)

  • Choi, Hyebin;An, Jaun;Kwon, Ki-Young
    • Applied Chemistry for Engineering
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    • v.33 no.4
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    • pp.436-439
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    • 2022
  • 𝛽-Hydroxynitrile and 𝛽-ketonitrile were synthesized by the electrochemical oxidation of benzyl alcohol in an acetonitrile solvent. 𝛽-Hydroxynitrile was prepared by the reaction between benzaldehyde from the oxidation of benzyl alcohol and acetonitrile anion which was produced from the electrochemical reduction of acetonitrile. 𝛽-Hydroxynitrile was finally electrochemically converted into 𝛽-ketonitrile by applying 20 mA of current for 3 h. We demonstrated that 𝛽-hydroxynitrile or 𝛽-ketonitrile syntheses were prepared by electrochemical oxidation of benzyl alcohol with a commonly used Pt electrode at room temperature.

Synthesis of Ru Incorporated TiO2 and Application to Oxidation of Benzyl Alcohol with Molecular Oxygen (Ru를 도입한 TiO2의 합성과 산소를 이용한 알코올 산화반응 연구)

  • Kim, Youngyeong;Choi, Myong Yong;Kwon, Ki-Young
    • Applied Chemistry for Engineering
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    • v.25 no.6
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    • pp.645-647
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    • 2014
  • We synthesized $TiO_2$ ($Ru_x/TiO_2$) incorporating $TiO_2$ and Ru via an one-step hydrothermal method. The physical properties were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The prepared samples were applied as a catalyst for the oxidation of benzyl alcohol to benzaldehyde using molecular oxygen ($O_2$). Especially, the catalytic activities increased as the contents of ruthenium in $TiO_2$ increased without the formation of any byproducts.

Synthesis of Pd/TiO2 Catalyst for Aerobic Benzyl Alcohol Oxidation (호기성 벤질 알코올 산화반응을 위한 팔라듐 이산화티타늄 촉매 개발)

  • Cho, Tae Jun;Yoo, Kye Sang
    • Applied Chemistry for Engineering
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    • v.25 no.3
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    • pp.281-285
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    • 2014
  • $Pd/TiO_2$ particles were prepared by wet impregnation for aerobic benzyl alcohol oxidation. Catalysts were prepared by the impregnation of 10 wt% palladium on $TiO_2$ after calcination at various temperatures. The surface areas of the catalysts were changed with calcination temperature. The catalyst calcined at $300^{\circ}C$ possessed the highest surface areas. Catalytic activity of the prepared samples was examined for aerobic benzyl alcohol oxidation. Among the samples, $Pd/TiO_2$ calcined at $300^{\circ}C$ showed the highest catalytic activity. Moreover, the catalysts with various Pd concentrations from 5 wt% to 15 wt% were prepared to investigate an optimum catalyst. 10 wt% $Pd/TiO_2$ was the most active in this reaction due to its higher surface areas and metal dispersion.

Synthesis of Pd-Ag on Charcoal Catalyst for Aerobic Benzyl Alcohol Oxidation Using [Hmim][PF6] ([Hmim][PF6]를 사용한 벤질 알코올의 호기성 산화반응용 팔라듐-은 차콜 촉매 제조)

  • Choo, Yunjun;Yoo, Kye Sang
    • Applied Chemistry for Engineering
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    • v.25 no.4
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    • pp.425-429
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    • 2014
  • Pd on charcoal particles were prepared by wet impregnation to develop commercial catalyst for aerobic benzyl alcohol oxidation. Especially, one of room temperature ionic liquids, [Hmim][$PF_6$], was used as an effective solvent in the synthesis to improve the metal dispersion of the catalysts. Among the Pd/Charcoal with various Pd concentrations, 7.5 wt% catalyst showed the higher catalytic activity and stability. Moreover, Ag was used as a promoter with various ratios in catalyst preparation. Under identical reaction conditions, the catalyst with 9 : 1 of Pd and Ag weight ratios was most active due to higher metal dispersion.

Kinetic Study on the Oxidation Reaction of Alcohols by Cr(VI)-Quinoline Compound (크롬(VI)-퀴놀린 화합물에 의한 알코올류의 산화반응에 대한 반응속도론적 연구)

  • Park, Young-Cho;Kim, Soo-Jong
    • Journal of Convergence for Information Technology
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    • v.11 no.9
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    • pp.109-114
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    • 2021
  • Cr(VI)-quinoline compound[(C9H7NH)2Cr2O7] was synthesized by the reaction between of quinoline and chromium(VI) trioxide, and structure was FT-IR, elemental analysis. The oxidation ability of benzyl alcohol greatly depends upon the dielectric constant of the used organic solvent, where carbon tetrachloride was worst and N,N'-dimethylformamide was best solvent. Noticeably, in N,N'-dimethylformamide solvent, Cr(VI)-quinoline compound oxidized substituted benzyl alcohols. The Hammett reaction constant(ρ)=-0.69(303K). As a resuit, Cr(VI)-quinoline compound was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones. Cr(VI)-quinoline compound was selective oxidizing agent of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary alcohol ones.