• Title/Summary/Keyword: alkylation

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Photochemical Synthesis of Aspartylphenylalanyl Methyl Ester (광 알킬화 반응에 의한 Aspartylphenylalanyl Methyl Ester의 합성)

  • Sang Chul Shim;Kyu Ho Chae
    • Journal of the Korean Chemical Society
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    • v.19 no.5
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    • pp.367-374
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    • 1975
  • Glycine residue in N-X-glycylphenylalanine methyl ester(X = trifluoroacetyl or acetyl) was converted into aspartic acid derivative by a photoalkylation reaction. The reaction was induced with 350 nm lamp using a combination of diacetyl/di-t-butyl peroxide (DBP) as the photoinitiator, and acetic anhydride as the alkylating agent. In the thermal reaction with DBP and acetic anhydride, the same alkylation reaction of the dipeptide was observed. From this thermal alkylation reaction the photoalkylation reaction is also thought to undergo via free radical mechanism.

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A Comparison of Standardization Methods in Near-infrared Analysis

  • Ko, Young-Hyun;Park, Kwang-Su;Lee, Hye-Seon;Jun, Chi-Hyuck;Ku, Min-Sik;Chung, Hoe-Il
    • Near Infrared Analysis
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    • v.1 no.1
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    • pp.9-17
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    • 2000
  • A variety of standardization methods between two near-infrared (NIR) spectrometers were investigated for the prediction of five constituents in trans-alkylation process. Spectra were collected by two different instruments (one is regarded as mater instrument, other on as slave instrument). Three well-known standardization methods of direct standardization (DS), piecewise direct standardization (PDS) and slope/bias correction of response variable were applied to trans-alkylation samples on the slave instrument. We have examined for a set of reliable standardization samples using smaller number of transfer samples in order to increase efficiency of standardization.

Introduction of a New Chiral Oxazolidin-2-one Derived from D-Mannitol and Its Applications as a Chiral Auxiliary

  • Kim, Si-Min;Jin, Hyun-Yong;Jun, Jong-Gab
    • Bulletin of the Korean Chemical Society
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    • v.23 no.5
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    • pp.749-757
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    • 2002
  • Chiral oxazolidin-2-one is easily prepared from D-mannitol and demonstrated to undergo highly diastereoselective alkylation reactions via lithium imide Z-enolates of its N-acyl derivatives to afford ${\alpha}-branched$ products. Evans syn and non-Evans sy n aldol products were also selectively obtained using this new auxiliary in high diastereomeric purity by simply changing the stoichiometry of TiCl4 and the nature of the amine base. Also, this new auxiliary is employed in diastereoselective Staudinger-type ${\beta}-lactam$ syntheses. Using 2-chloro-1-methylpyridinium iodide as the dehydrating agent, the reaction of auxiliary tethered acetic acid with trans imines gave the desired ${\beta}-lactams$ with cis-selectivity.

Synthesis of (2,7-dibromo-9,9-dialkyl-substituted-fluorene)s for Poly(dialkylfluorene)s by Phase Transfer Catalytic Reaction

  • Kwon, Seung-Ho;Kim, Jin-Sung;Park, Ji-Ho;Yoo, Jae-Soo
    • 한국정보디스플레이학회:학술대회논문집
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    • 2002.08a
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    • pp.724-727
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    • 2002
  • 2,7-dibromo-9, 9-dialkyl-substituted-fluorene derivatives were prepared by the alkylation of 2,7-dibromofluorene with various alkyl groups under two-phase phase transfer catalysis (PTC) conditions, as monomers for synthesizing poly(dialkylfluorene)s. Tetra-nbutylammonium hydrogen sulfate (TBAHS) was used as a phase transfer catalyst to enhance nucleophilic substitution. In addition, NaOH in water (25M) was used as a base to generate anions. Compared to conventional alkylation using butyllithium(BuLi), the reaction using the PTC technique attained high selectivity and substantial conversion of reactants, due to the enhanced reaction rate, while the reaction was carried out under moderate conditions. An approximately 90% yield was obtained from the reaction and the reaction time was remarkably reduced. 2,7-dibromo-9,9-dihexyl-fluorene, 2,7-dibromo-9,9-dioctyl-fluorene, and 2,7-dibromo-9,9-di(2-ethylhexyl)-fluorene were effectively synthesized by phase transfer catalytic reaction.

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Selective alkylation of alkylaromatics over HZSM-5 zeolite synthesised in fluoridemedium (Fluoridemedium에서 HZSM-5 제올라이트를 이용한 알킬아로마틱의 선택적 알킬화)

  • Hemalatha, Pushparaj;Venkatachalam, Kandan;Ganesh, Mani;Peng, Mei-Mei;Lee, Joo-Bo;Jang, Hyun-Tae
    • Proceedings of the KAIS Fall Conference
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    • 2011.05a
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    • pp.323-326
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    • 2011
  • HZSM-5, synthesized in fluoride medium, showed high selectivity for the formation of 1,4-diethylbenzene (1,4-DEB) in the vapour phase ethylation of ethylbenzene (EB) with ethanol and hence becomes a convenient eco-friendly substitute for hazardous mineral acid catalysts. De-ethylation of EB to benzene was also minimized over this catalyst. As the medium pore size and presence of weak and medium acid sites might be the cause of such benefits, fluoride mediated synthesis of ZSM-5 is proven to be advantageous for para-selective alkylation of alkyl aromatics.

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A Stereoselective Asymmetric Synthesis of Antibiotic (-)-Fumagillol Using Claisen Rearrangement and Intramolecular Ester Enolate Alkylation as Key Steps

  • Kim Deukjoon;Ahn Soon Kil;Bae Hoon;Kim Hak Sung
    • Archives of Pharmacal Research
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    • v.28 no.2
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    • pp.129-141
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    • 2005
  • (-)-Fumagillol (1), a hydrolysis product of fumagillin, has been synthesized by several group from commercially available 1,2:5,6-di-O-isopropylidene-${\alpha}$-D-allofuranose in a highly stereoselective manner. Chiral centers on C5 and C6 came from D-allofuranose and the asymmetric center on C4 was accomplished by 1,3-chirality transfer using the Claisen rearrangement on a chiral allyl alcohol. Chirality, which is necessary on an epoxide consisting of the spiro-ring system, was diastereoselectively constructed by the well-known reaction, intramolecular ester enolate alkylation (IEEA), which showed that this reaction can be applied to the alpha-alkoxy ester system. The epoxide on the side chain was regioselectively introduced by the difference between the number of substituents on the vinyl groups. This accomplishment proved that IEEA can be a useful tool for the synthesis of complex molecules.

Synthesis of 4-Phenyltetralone Derivatives and Reaction Mechanism

  • Kwon, Soon-Kyoung;Park, Young-Nam
    • Archives of Pharmacal Research
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    • v.23 no.4
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    • pp.329-331
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    • 2000
  • 4-(p-Chlorophenyl)tetralone (6) and 7-chloro-5-(p-chlorophenyl)tetralone (9) are key intermediates for the development of benzazepinone derivative haftens. These compounds could be synthesized from 4-phenyltetralone derivatives by triflic acid catalyzed Friedel-Crafts reaction. The reaction mechanism of Friedel-Crafts alkylation/acylation with lactones in triflic acid is presented. According to our tentative research, ring opening of protonated lactone (2) occurs in alkyl cleavage and the rate of the reaction is not dependent on concentration of triflic acid. So, alkylation of lactone in Friedel-Crafts reaction is presumed to be $A_{AL}$ 1. In second step, intramolecular acylation of the intermediates 4 to 6, 4 can be transformed to a triflic acid-carboxylic anhydride and then the cyclization is undergone after leaving of the triflate anion.

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Solvent-free Microwave-Assisted Ortho-Alkylation of Aromatic Ketimine with Acrylic Acid Derivatives by Rh(I) Catalyst

  • Jo, Eun-Ae;Ahn, Jeong-Ae;Jun, Chul-Ho
    • Bulletin of the Korean Chemical Society
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    • v.28 no.11
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    • pp.2020-2024
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    • 2007
  • The article reports the synthesis of a novel bispyridino-18-crown-6 ether, 7-{[(5S,15S)-5,15-diphenyl- 3,6,14,17-tetraoxa-23,24-diazatricyclo[17.3.1.18,12]tetracosa-1(23),8(24),9,11,19,21-hexaen-10-yl]oxy}heptylferrocenamide 6, bearing the C2-symmetric diphenyl substituents as chiral barriers and the ferrocenyl groups serving as an electrochemical sensor, and its electrochemical study with D- and L-AlaOMe·HCl as the guest by cyclovoltametry.