• Title/Summary/Keyword: bromination

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Halogen Containing Heterocyclic Compounds (Part Ⅱ) Halogenation of Furfuryl Derivatives-Maleic Anhydride Adduct (含할로겐 異元素環化合物에 關한 硏究 (第2報) 풀퍼릴誘導體-마레인酸無水物 附加物의 할로겐化反應)

  • Kim, You-Sun;Kim, Chung-Hee
    • Journal of the Korean Chemical Society
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    • v.9 no.2
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    • pp.88-95
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    • 1965
  • The exo adduct between furfuryl derivatives (furan, furfuryl acetate and furfuryl alcohol) and maleic anhydride were prepared in the presence of ethyl ether. The bromination of the exo adduct of each derivatives gave a monobromolactone and dibromoacid when the reaction was done in the presence of water. The formation of the bromolactone was proved to be dependent to the carboxylic participation to the incipient rearranged carbonium ion of a classical type, and the participation was sterically hindered by the steric structure of the substituents. The bromination of the furan-maleic anhydride adduct in the presence of organic solvent $(CCl_4,\;CH_2Cl_2)$ gave the dibromide, whereas the photochlorination of the same adduct in the presence of carbon tetrachloride gave the tetrachloride. The procedure of the preparation and the reaction path of the halogenation were described.

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Synthesis of Novel 9-Fluoroanthracycline Derivatives

  • Rho, Young S.;박시호;Kim, Sun Y.;조인호;이철현;정채준;Kang, Heun S.
    • Bulletin of the Korean Chemical Society
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    • v.19 no.1
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    • pp.74-78
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    • 1998
  • Synthesis of novel 9-fluoroanthracyclines carrying L-fucose as a sugar component is described. Compound 3 containing a fluorine at the C-9 position was synthesized from an epoxide 2 and HF/Pyr (7 : 3). Bromination and hydrolysis of compound 3 resulted in synthesis of an aglycone, 9-fluoroanthracyclinone 6. The α-(1b) and β -anomers (1a) of the final product were obtained in high yields by a coupling reaction with the L-fucose.

Synthesis and Ring-Opening Polymerization of 1,2-Disubstituted Cyclobutanes

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • v.7 no.3
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    • pp.210-213
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    • 1986
  • 1,1-Dicyano-2-ethoxycyclobutane (1a) was prepared by [2 + 2] cycloaddition reaction of vinylidene cyanide with ethyl vinyl ether. 1,1-Dicyano-2-phenylcyclobutane (1b) was prepared by the reactions involving the reduction of cinnamyl alcohol, chlorination, cyanomethylation, bromination, and ring-closure reaction. Compound 1a was ring-opening polymerized with NaCN or n-butyllithium to give a low molecular weight polymer. The compound 1b however, failed to polymerize by either anionic or radical catalysts.

Synthesis of 1,1,3,4-Tetramethyl-1-sila-2,4-Cyclopentadiene

  • Joo, Wan-Chul;Hwang, Hae-Sook;Hong, Jang-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.6 no.6
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    • pp.348-350
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    • 1985
  • The compound 1,1,3,4-tetramethyl-1-sila-3-cyclopentene was obtained through the reaction of 2,3-dimethylbutadiene and dichlorodimethyl-silane in THF in the presence of sodium metal. After the bromination of this compound at $0^{\circ}C$ for 2 hrs and dehydrobromination by using a base, we prepared 1.1.3.4-tetramethyl-1-sila-2,4-cyclopentadiene, Which could undergo dimerization. The identification has been done by using $^1H-,^{13}C-$ and C/H-Correlation two dimensional nmr spectroscopies.

Halogenation of Aldehydes and Ketones by Selenium (IV) Oxyhalides Generated in-situ from Selenium Dioxide and Halotrimethylsilanes

  • 이종근;박인수;서종화
    • Bulletin of the Korean Chemical Society
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    • v.16 no.4
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    • pp.349-355
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    • 1995
  • Bromo-and chlorotrimethylsilane react with selenium dioxide in halocarbon solvents and generate selenium oxybromide and oxychloride, respectively. These in-situ generated oxyhalides turned out to be very efficient for selective bromination and chlorination of aldehydes and ketones. Under carefully controlled reaction conditions, second and third introduction of halogens into carbonyl compounds can be greatly suppressed, and high yields of monohalo compounds were obtained. The product ratios of this halogenation reactions can be best explained if the reactions are assumed to involve intermediate β-ketoselenenyl chlorides.

Preparation and Gas Characterization of Poly(phenylene oxide) Containing Imidazolium (이미다졸륨을 포함하는 폴리페닐렌옥사이드 고분자 제조 및 기체 특성평가)

  • Son, Tae Yang;Jo, Jin Woo;Kim, Ji Hyeon;Kim, Tae Hyun;Tocci, Elena;Nam, Sang Yong
    • Membrane Journal
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    • v.27 no.6
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    • pp.528-535
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    • 2017
  • In this study, halogen element was introduced into polyphenylene oxide polymer using bromination reaction, and then halogen element was replaced with imidazolium. Imidazolium corporated polyphenylene oxide polymer was synthesized and the synthesis was confirmed by various instrumental characterization. In addition, gas permeation properties of $O_2$, $N_2$, $CO_2$ were studied with different imidazolium contents. As the content of imidazolium increased, the ion exchange capacity increased and the mechanical strength decreased. The gas permeance showed a tendency to decrease slightly with increaing imidazolium contents. Whereas, it was confirmed that the tendency of $CO_2/N_2$ ideal selectivity increased as the imidazolium contents increased.

Functional Analyses and Application of Microbial Lactonohydrolases

  • Shimizu, Sakayu;Honda, Kohsuke;Kataoka, Michihiko
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.7 no.3
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    • pp.130-137
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    • 2002
  • Microbial lactonohydrolases (intramolecular ester bond-hydrolyzing enzymes) with unique properties were found. The lactonohydrolase from Fusarium oxysporum catalyzes enantiose-lective hydrolysis of aldonate lactones and D-pantoyl lactone (D-PL). This enzyme is useful for the large-scale optical resolution of racemic PL. The Agrobacterium tumefaciens enzyme catalyzes asymmetric hydrolysis of PL, but the stereospecificity is opposite to that of the Fusarium enzyme. Dihydrocoumarin hydrolase (DHase) from Acinetobacter calcoaceticus is a bifunctional enzyme, which catalyzes not only hydrolysis of aromatic lactones but also bromination of monochlorodi-medon in the presence of H$_2$O$_2$and dihydrocoumarin. DHase also hydrolyzes several linear esters, and is useful for enantioselective hydrolysis of methyl DL-$\beta$-acetylthioisobutyrate and regioselective hydrolysis of methyl cetraxate.

Synthesis of Ketoconazole Derivatives

  • Ryu, Jae-Chun;Lee, Kwang-Jae;Lee, Sang-Hee
    • Bulletin of the Korean Chemical Society
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    • v.24 no.4
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    • pp.460-466
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    • 2003
  • For the drug master file (DMF) of ketoconazole, four impurities (1-4) contained in ketoconazole were synthesized. During the synthesis of 2, a new synthetic method of 1,4-dihydropyrazine was established. To oxidize the aminoalcohol (2j) to the aminal (2j-1), the standard Swern oxidation condition was modified to mask the nucleophilicity of the amino group temporarily using one equivalent of acetic acid. Derivative 3 was synthesized via regioselective bromination at the 2 position of the 4-aminophenol derivative (3a) using $Br_2$ in the presence of p-TsOH. The etherification of aryl bromide with the phenol derivative (1f) was accomplished by a modification of the general Cu-mediated reaction condition using excess 1f itself as a solvent at elevated temperature (190 ℃).