• Title/Summary/Keyword: Trimethylsilyl ethers

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An Efficient Method for Selective Deprotection of Trimethylsilyl Ethers and Tetrahydropyranyl Ethers under Solvent-free Conditions

  • Hajipour, A.R.;Bagheri, Hamid R.;Ruoho, Arnold E.
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1689-1691
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    • 2005
  • 1-Butyl-4-aza-1-azoniabicyclo[2.2.2]octane dichromate (BAABOD) 3 is a useful reagent for the selective cleavage of trimethylsilyl ethers and tetrahydropyranyl ethers to their corresponding aldehydes and ketones in the presence of $AlCl_3$ under solvent-free conditions. This method is very simple and efficient and the reaction has been carried out under solvent-free conditions in the presence of a catalytically amount of aluminum chloride.

Comparative Studies on Two Types Derivatives of Gibberellins for the Gibberellin Analysis by Gas Chromatography-Selected Ion Monitoring (GC-SIM에 의한 두종의 gibberellin유도체의 분석)

  • Park, Keun-Hyung
    • Applied Biological Chemistry
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    • v.28 no.2
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    • pp.82-87
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    • 1985
  • Aiming at the improvement of accuracy and sensitivity of gibberellin analysis by gas chromatography-selected ion monitoring (GC-SIM), the mass spectra of two types of 29 gibberellin derivatives, methyl ester-trimethylsilyl ethers and trimethylsilyl ester-trimethylsilyl ethers, were obtained and their advantages and disadvantages in GC-SIM analysis are discussed.

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A Direct Comparison Study of Asymmetric Borane Reduction of C=N Double Bond Mediated by Chiral Oxazaborolidines

  • Cho Byung Tae;Ryu, Mi Hae;Chun Yu Sung;Dauelsberg Ch.;Wallbaum Sabine;Martens Jurgen
    • Bulletin of the Korean Chemical Society
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    • v.15 no.1
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    • pp.53-57
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    • 1994
  • A comparison study on asymmetric borane reduction of ketoxime ethers and N-substituted ketimines possesing C = N double bond mediated by the selected chiral oxazaborolidines (1-6) was investigated. Thus, an aromatic ketoxime O-alkyl ether acetophenone oxime O-methyl ether was reduced to the corresponding amine (1-phenylethylamine 8a) with optical yields, such as 58% ee with 1, 86% ee with 2, 3% ee with 3, 99% ee with 4, 60% ee with 5, and 73% ee with 6. However, the reduction of an aliphatic ketoxime derivative 2-heptanone oxime O-methyl ether provided low optical inductions (7-13% ee). For ketoxime O-trimethylsilyl ethers, the reduction of acetophenone O-trimethylsilyl ether afforded 8a with optical yields which were 90% ee with 1, 40% ee with 2, 2% ee with 3, 62% ee with 4, 5% ee with 5, and 60% ee with 6. The reduction of 2-heptanone O-trimethylsilyl ether also gave the product amine with low optical yields (10-40% ee). In the case of N-substituted ketimines, the reduction of acetophenone N-phenylimine afforded the corresponding amine with 79% ee, 78% ee, 9% ee, 73% ee, 78% ee and 67% ee using 1, 2, 3, 4, 5, and 6, respectively, whereas low optical inductions (5-18% ee) for 2-heptanone N-phenylimine were achieved.

Mild and Efficient Silylcyanation of Aldehydes Catalyzed by Zirconium Complex

  • Kim, Sung-Soo;Lee, Jun-Tae;Song, Dae-Ho;Lee, Ik-Mo;Park, Sun-Young
    • Bulletin of the Korean Chemical Society
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    • v.26 no.2
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    • pp.265-267
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    • 2005
  • An efficient method of addition of trimethylsilyl cyanide to aldehydes by employing a zirconium complex as the catalyst has been described. A variety of aromatic, aliphatic, cyclic and heterocyclic aldehydes has been converted into corresponding trimethylsilyl ethers in excellent yield within short reaction time.

Cyanosilylation of Carbonyl Compounds Catalyzed by Potassium L-Aspartate

  • George, Soney C.;Kim, Sung-Soo;Kim, Ho-Sub
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2431-2434
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    • 2007
  • Potassium L-aspartate has been used as a catalyst for the cyanosilylation of carbonyl compounds producing corresponding cyanohydrin trimethylsilyl ethers in excellent yield of up to 98%. Although the catalyst is chiral, the enantioselectivities observed are generally poor except for one case, α-naphthaldehyde, 89% ee.

Novel Naphthalene Based Lariat-Type Crown Ethers Using Direct Single Electron Transfer Photochemical Strategy

  • Park, Hea Jung;Sung, Nam Kyung;Kim, Su Rhan;Ahn, So Hyun;Yoon, Ung Chan;Cho, Dae Won;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3681-3689
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    • 2013
  • This study explored a direct SET-photochemical strategy to construct a new family of thioene conjugated-naphthalamide fluorophore based lariat-crown ethers which show strong binding properties towards heavy metal ions. Irradiations of designed nitrogen branched (trimethylsilyl)methylthio-terminated polyethylenoxy-tethered naphthalimides in acidic methanol solutions have led to highly efficient photocyclization reactions to generate naphthalamide based lariat type thiadiazacrown ethers directly in chemo- and regio-selective manners which undergo very facile secondary dehydration reactions during separation processes to produce their corresponding amidoenethio ether cyclic products tethered with electron donating diethyleneoxy- and diethyenethio-side arm chains. Fluorescence and metal cation binding properties of the lariat type enamidothio products were examined. The photocyclized amidoenethio products, thioene conjugated naphthalamide fluorophore containing lariat-thiadiazacrowns exhibited strong fluorescence emissions in region of 330-450 nm along with intramolecular exciplex emissions in region of 450-560 nm with their maxima at 508 nm. Divalent cation $Hg^{2+}$ and $Pb^{2+}$ showed strong binding to sulfur atom(s) in side arm chain and atoms in enethiadiazacrown ether rings which led to significant enhancement of fluorescence from its chromophore singlet excited state and concomitant quenching of exciplex emission. The dual fluorescence emission responses towards divalent cations might provide a new guide for design and development of fluorescence sensors for detecting those metals.

Simultaneous Gas Chromatography-Mass Spectrometric Determination of Total and Individual Phthalic Esters Utilizing Alkaline Hydrolysis and Silyl Derivatization Technique

  • Kim, Min-Seon;Li, Dong-Hao;Shim, Won-Joon;Oh, Jae-Ryoung;Park, Jong-Man
    • Bulletin of the Korean Chemical Society
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    • v.28 no.3
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    • pp.432-438
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    • 2007
  • Environmentally important phthalic esters have been analyzed by GC-MS in terms of individual phthalic esters or total phthalic esters directly or after derivatization. Derivatization improves the chromatographic characteristics of the highly polar phthalic esters. This study focused on the GC-MS determination of the total phthalic esters and the individual phthalic esters simultaneously. The phthalic esters were hydrolyzed to phthalate and corresponding alcohols in 1 M NaOH solution at 90 oC for 30 min followed by extraction with ethyl acetate after acidifcation. The phthalic acid and alcohols were simultaneously silyl derivatized using bis(trimethylsilyl)trifluoroacetamide (BSTFA) to their corresponding silyl ester and ethers in the mixture of 60% acetone and 40% ethyl acetate at room temperature within 30 min. Because of the high reactivity of BSTFA with the phthalic acid and alcohols effective silyl derivatization was possible simultaneously. GC-MS analysis of the silyl derivatives of phthalic acid and alcohols was performed. The total phthalic ester content was estimated from the analytical result of phthalic silyl ester, while the individual phthalic ester was quantified from the analytical results of alcoholic silyl ethers. This technique was applied to spiked tab water and real seawater samples from the Lake Shihwa in Korea. The results were checked against the results from the direct GC-MS analysis of the phthalic esters and reasonable recoveries with high sensitivity were achieved. The recoveries were higher than 75% with low relative standard deviation (below 10%).