• Title/Summary/Keyword: Bromide ($Br^-$)

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Efficient Cleavage of Alkyl Aryl Ethers Using an Ionic Liquid under Microwave Irradiation

  • Park, Se Kyung;Battsengel, Oyunsaikhan;Chae, Junghyun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.174-178
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    • 2013
  • A highly reliable dealkylation protocol of alkyl aryl ethers, whose alkyl groups are longer than methyl group, has been developed. We report that various ethyl, n-propyl, and benzyl aryl ethers are successfully cleaved using an ionic liquid, 1-n-butyl-3-methylimidazolium bromide, [bmim][Br], under microwave irradiation. Despite many characteristics such as lower cost and less toxicity of the alkylating agents, and greater hydrophobicity of the products, longer alkyl ethers have been significantly less exploited than methyl ethers, probably due to more difficulty in the deprotection step. Since it has the same advantages as the demethylation method developed by this group including mild conditions, short reaction time, and small use of the ionic liquids, the dealkylation protocol can greatly encourage the broader use of longer alkyl groups in the protection of phenolic groups. As with our previous study of demethylation using [bmim][Br], the microwave irradiation is crucial for the deprotection of longer alkyl aryl ethers. Unlike the conventional heating, which causes either low conversion or decomposition, the microwave irradiation seems to more effectively provide energy to cleave the ether bonds and therefore suppresses the undesired reactions.

A Gas Phase Kinetic Study on the Thermal Decomposition of $ClCH_2CH_2CH_2Br$

  • Kim, Sung-Hoon;Choo, Kwang-Yul;Jung, Kyung-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.10 no.3
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    • pp.262-269
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    • 1989
  • The gas phase thermal decomposition of 1-bromo-3-chloropropane in the presence of radical inhibitor was studied by using the conventional static system. The mechanism of unimolecular elimination channel is shown below. [...] In this scheme, the total molecular dissociation rate constant, ($k_1\;+\;k_2$), for the decomposition of $BrCH_2CH_2CH_2Cl$ was determined by pyrolyzing the $BrCH_2CH_2CH_2Cl$ in the temperature range of $380-420^{\circ}C$ and in the pressure range of 10∼100 torr. To obtain $k_3\;and\;k_4,\;and\;to\;obtain\;k_1\;and\;k_2$ independently, the thermal decompositions of allyl chloride and allyl bromide were also studied. The Arrhenius parameters for each step are as follows; $log\;A_{\infty}\;=\;14.20(sec^{-1}),\;E_a$ = 56.10(kcal/mol) for reaction path 1; $log\;A_{\infty}\;=\;12.54(sec^{-1}),\;E_a$ = 49.75(kcal/mol) for reaction path 2; $log\;A_{\infty}\;=\;13.41(sec^{-1}),\;E_a$ = 50.04(kcal/mol) for reaction path 3; $log\;A_{\infty}\;=\;12.43(sec^{-1}),\;E_a$ = 52.78(kcal/mol) for reaction path 4; Finally, the experimentally observed pressure dependence of the rate constants in each step is compared with the theoretically predicted values that are obtained by the RRKM calculations.

Heat transfer study of double diffusive natural convection in a two-dimensional enclosure at different aspect ratios and thermal Grashof number during the physical vapor transport of mercurous bromide (Hg2Br2): Part I. Heat transfer

  • Ha, Sung Ho;Kim, Geug Tae
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.32 no.1
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    • pp.16-24
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    • 2022
  • A computational study of combined thermal and solutal convection (double diffusive convection) in a sealed crystal growth reactor is presented, based on a two-dimensional numerical analysis of the nonlinear and strongly coupled partial differential equations and their associated boundary conditions. The average Nusselt numbers for the source regions are greater than those at the crystal regions for 9.73 × 103 ≤ Grt ≤ 6.22 × 105. The average Nusselt numbers for the source regions varies linearly and increases directly with the thermal Grashof number form 9.73 × 103 ≤ Grt ≤ 6.22 × 105 for aspect ratio, Ar (transport length-to-width) = 1 and 2. Additionally, the average Nusselt numbers for the crystal regions at Ar = 1 are much greater than those at Ar = 2. Also, the occurrence of one unicellular flow structure is caused by both the thermal and solutal convection, which is inherent during the physical vapor transport of Hg2Br2. When the aspect ratio of the enclosure increases, the fluid movement is hindered and results in the decrease of thermal buoyancy force.

Removal of Cu impurities in LiBr solution using cyclone electrowinning method (싸이클론 전해환원방법을 이용한 LiBr 용액내의 Cu 불순물 제거에 관한 연구)

  • Da Jung Park;Kyu Hwan Lee
    • Journal of the Korean institute of surface engineering
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    • v.57 no.2
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    • pp.92-97
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    • 2024
  • The LiBr aqueous solution, which is the absorption liquid of absorption refrigerator, must be replaced periodically because the concentration of impurities such as Cu2+, Fe2+, Ca2+, etc., increases due to corrosion of the tubes as the period of use increases, and the refrigeration efficiency decreases significantly. In order to reuse the waste absorption liquid, flocculation-precipitation method is mainly applied to precipitate the impurities, which requires hundreds of times the concentration of impurities and generates additional waste. In this study, a process for removing Cu ion impurities from cyclone electrolyzer by electrolytic reduction is presented in a small-scale facility without additional waste. It was confirmed that Cu ion impurities can be removed down to 1 ppm by electrolytic reduction process, and to further improve the removal rate, the mass transfer rate was increased by using a cyclone electrolyzer. The removal rate of Cu ions increased with the increase of flow rate and current density, and it was confirmed that Cu was removed at a rate of 1.48 ppm/h under the condition of 330 mL/sec and 2.5 mA/cm2.

Zinc Mediated Barbier Type Allylation of Cyclic Imides and Subsequent Coupling Reactions with Carbon Nucleophiles

  • Kang, Seok-Won;Heo, Eun-Young;Jun, Jong-Gab;Kim, Sung-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.12
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    • pp.1924-1928
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    • 2004
  • Allylations of N-benzyl and N-methyl cyclic imides were accomplished successfully under mild Barbier type conditions using zinc metal, allyl bromide and catalytic amount of $PbBr_2$. Subsequent coupling reactions with some carbon nucleophiles afforded 1,2- and 1,4-addition products in moderate to high yields.

Halogenation of Resorcinol Derivatives

  • Baek Seung-Hwa
    • Bulletin of the Korean Chemical Society
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    • v.9 no.1
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    • pp.13-15
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    • 1988
  • Several types of resocinols have been monobrominated in the ring in good yields with sodium bromide in the presence of 18-crown-6 on oxidation with m-chloroperbenzoic acid. Monoiodination takes place with 2'-(1-methylcyclohexen-3-yl)-5-(1,1-dimethylheptyl )-resocinol when sodium iodide is employed. This new reagent system, MX/18-crown-6/m-CPBA (M =$K^+, Na^+, X = Br^-, I^-X$ ), effects the regiospecific halogenation of activated aromatic ring over olefinic double bond.

Acustic Study on the Kinetics for the Dissociation-Recombination Reaction between Micelle and Counter-ion in Dodecyl Pyridinium Bromide Solution (Dodecyl Pyridinium Bromide 水溶液中의 Micelle과 Counter-Ion 間의 解離-再結合反應에 對한 超音波에 依한 反應速度論的 硏究)

  • Lee Kun Moo
    • Journal of the Korean Chemical Society
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    • v.17 no.2
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    • pp.73-79
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    • 1973
  • The ultrasonic absorption of Dodecyl pyridinium bromide (D.P.B.) in aqueous solution has been measured at $20^{\circ}C$ over a range of frequencies between 0.1 mc and 90 mc and a range of concentrations from 5 to 100 mM. The excess absorption was observed only in the solutions the concentration of which was higher than the critical micellar concentration (c.m.c.) both in the presence and absence of salt. The excess absorption of sound and the relaxation frequencies obtained from the absorption curves show a discontinuity with the variation of the concentration of D.P.B. in the neighborhood of 60 mM. Other properties such as viscosity, conductivity and velocity of sound also exhibit such a change near the same concentration. It is concluded that a change in the properties of the micelles of D.P.B. occurs in the neighborhood of this concentration. The mechanism of the observed ultrasonic excess absorption in attributed to the reaction $M_2{\rightleftarrow}M_1+2Br^-$where$M_2$ and$M_1$are two types of micelles. The rate constants of forward and backward reactions are found to be $6.9 {\times} 10^5 sec^{-1)$and $6.7{\times}10^{10}sec^{-1}mole{-2}$ respectively. Some kinetic characteristics including free energy, enthalpy, entropy and activation energy were calculated.

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Physicochemical Properties of Oxidized Rice Flour and Effects of Added Oxidized Rice Flour on the Textural Properties of Julpyun(Korean traditional rice cake) during Storage (TEMPO를 이용하여 산화시킨 쌀가루의 이화학적 특성 및 산화 쌀가루를 첨가한 절편의 저장 중 텍스처 특성)

  • Kim, Moon-Soo;Suh, Dong-Soon;Chang, Pahn-Shick;Kim, Kwang-Ok
    • Korean Journal of Food Science and Technology
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    • v.33 no.2
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    • pp.209-215
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    • 2001
  • This study was conducted to examine the effects of 2,2,6,6-tetramethyl-1-piperidine oxoammonium ion(TEMPO) and sodium bromide(NaBr) for the selective oxidation on primary alcohol groups of rice starch molecules in rice flour and to use oxidized rice flour in Julpyun to extend its shelf life. Reaction time decreased with higher levels of TEMPO and NaBr. Yield and selectivity decreased with increased NaBr levels. TEMPO increased yield until certain levels, but decreased thereafter. The levels of TEMPO and NaBr for the preparation of oxidized rice flour were determined as 0.9 and 44 mM/100 mM anhydroglucose unit, respectively. Water and oil binding capacities, and viscosity increased significantly by the oxidation of rice flour. The partial replacement of rice flour with oxidized rice flour increased peak viscosity and decreased setback. Oxidized rice flour with the increased amount of water showed positive effect on the textural properties of Julpyun during storage.

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Solubilization of Benzenesulfonate anion and Its Derivatives by the Micellar System of TTAB (TTAB 용액에서 Benzenesulfonate 음이온과 유도체들의 가용화에 대한 연구)

  • Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.45 no.1
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    • pp.7-13
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    • 2001
  • The interaction of benzenesulfonate anion and its derivatives ($C_6H_5SO_3^-, p-$CH_3C_6H_4SO_3^-, and $p-C_2H_5C_6H_4SO_3^-$) with the micellar system of cationic surfactant TTAB(tetradecyltrimethylammonium bromide) was studied by UV/Vis spectrophotometric method. The solubilization constants($K_s$) of benzenesulfonate anions into the micellar phase of this surfactant have been measured with the change of temperature. The effects of additives(n-pentanol and NaBr) on the solubilization of benzenesulfonate anions by this surfactant system have been also measured. There was a great decrease on the values of $K_s$ and CMC simultaneously with these additives so that the measured values of ln$K_s$ were linear relationships with the values of lnCMC. For the thermodynamic study, various thermodynamic parameters(${\Delta}G^0_s$, ${\Delta}H^0_s$ and ${\Delta}S^0_s$) have been calculated and analyzed from the dependence of Ks values on temperature.

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Study on the Solubilization of Phenoxide Anion by Mixed Surfactant Systems of CTAB and TTAB (CTAB/TTAB 혼합계면활성제에 의한 Phenoxide 음이온의 가용화에 대한 연구)

  • Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.44 no.3
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    • pp.177-183
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    • 2000
  • The interaction of phenoxide anion with .the mixed micelles of CTAB(Cetyl-trimethylammonium bromide) and TTAB(Tetradecyltrimethylammonium bromide) was studied by UV/Vis spectrophotometric method. The solubilization constants($K_s$) of phenoxide anion into the mixed micellar phase and the critical micellar concentrations(CMC) of those mixed surfactant systems have been measured and analyzed with the change of overall mole fraction of CTAB($\alpha_{CTAB}$) The effects of additives(n-pentanol and NaBr) on the solubilization of phenoxide anion by those mixed surfactant systems have been also measured. There was a great decrease on the values of solubilization constant and CMC with these additives. For the thermodynamic study, the dependence of $K_s$ values on temperature has been measured and various thermodynamic parameters(${\Delta}G^0_s$, ${\Delta}H^0_s$ and ${\Delta}S^0_s$) have been also calculated. The results show that all the values of ${\Delta}G^0_s$ and ${\Delta}H^0_s$ are negative within the measured temperature region but the values of ${\Delta}S^0_s$ are positive.

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