• 제목/요약/키워드: trimethylsilyl

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1,1-Dimethyl-2,5-bis(trimethylsilyl)-3,4-diphenyl-1-silacyclopenta-2,4-diene의 합성 (Synthesis of 1,1-Dimethyl-2,5-bis(trimethylsilyl)-3,4-diphenyl-1-silacyclopenta-2,4-diene)

  • 공영건;주완철
    • 대한화학회지
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    • 제30권6호
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    • pp.521-525
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    • 1986
  • Phenyltrimethylsilylacetylene과 리듐의 반응으로 부터 1,4-bis(trimethylsilyl)-2,3-diphenyl-1,4-butadene dianion이 형성되었다. 이 반응생성물과 dichlorodimethylsilane을 반응시키면 1,1-dimethyl-2,5-bis(trimethylsilyl)-3,4-diphenyl-1-silacyclopenta-2,4-diene이 얻어졌다. 이와 함께 분리된 1,4-bis(trimethylsilyl)-2,3-diphenyl-1,3-butadiene은 알칼리 매질에서 가수분해되어 생성된 화합물로 보인다.

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Efficient Preparation of 3-Fluoropyrrole Derivatives

  • Kim, Bo-Mi;San, Quan-Ze;Bhatt, Lok Ranjan;Kim, Sung-Kwon;Chai, Kyu-Yun
    • Bulletin of the Korean Chemical Society
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    • 제31권1호
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    • pp.31-34
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    • 2010
  • Noble N-substituted-3-fluoropyrroles derivatives were prepared from new precursor via ring formation. The addition reaction of ethyl iododifluoroacetate to vinyl trimethylsilane under the Cu(0) catalyst resulted in the formation of ethyl-2,2-difluoro-4-iodo-4-(trimethylsilyl)butanolate, which reacted with diisobutylaluminium hydride at $-30^{\circ}C$ to yield 2,2-diflouro-4-iodo-4-(trimethylsilyl)butanal. Finally, a series of N-substituted-3-fluoropyrrole derivatives were synthesized by the reaction of 2,2-diflouro-4-iodo-4-(trimethylsilyl)butanal with $NH_4OH$ or primary amines followed by reaction with KF solution.

Synthesis and Reactivity of Dinuclear Ni(II) Azido Complexes Containing Bithienylene or Terthienylene Bridging Ligands

  • Kim, Yong-Joo;Lee, Hyuck-Hee;Zheng, Zhen Nu;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • 제32권9호
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    • pp.3239-3244
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    • 2011
  • Dinuclear Ni(II)-thiophene halides, which contain linear bridging thienylenes, trans,trans-[$(PR_3)_2$(X)Ni-Y-Ni(X)$(PR_3)_2$] {X = Cl, Br; $H_2Y$ = 5,5'-dichloro-2,2'-bithiophene ($H_2bth$); $H_2tth$ = 5,5"-dichloro-2,2':5',2''-terthiophene ($H_2tth$)} were prepared by the oxidative addition of dihalobithiophene ($H_2bth$) or dihaloterthiophene ($H_2tth$) to [$Ni(COD)_2$] in the presence of tertiary phosphines. Subsequent reactions of $NaN_3$ with the dinuclear Ni(II)-thiophene chlorides gave the corresponding Ni(II)-azido complexes, trans,trans-[$(PR_3)_2(N_3)$Ni-Y-Ni$(N_3)(PR_3)_2$], whose reactivity toward trimethylsilyl pseudohalides such as trimethylsilyl isothiocyanates and cyanides was investigated. In addition, the reaction of trans-[$BrNi(PEt_3)_2-C_4H_2S-C_4H_2S$-CHO], a thienyl Ni(II) complex containing a terminal aldehyde group, with phosphonium ylide was examined.

Synthesis of 2-n-Butyl-3-fluoropyrrole Derivatives

  • Kim, Bo-Mi;San, Quan-Ze;Bhatt, Lok Ranjan;Jung, Dong-Woon;Lee, Young-Hang;Chai, Kyu-Yun
    • Bulletin of the Korean Chemical Society
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    • 제30권6호
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    • pp.1293-1296
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    • 2009
  • A new series of N-substituted 2-n-butyl-3-fluoropyrroles were prepared by a simple one-pot reaction designed of retrosynthesis. $\alpha,\alpha-Difluoro-\gamma-iodo-\gamma$-(trimethylsilyl)propyl n-butyl ketone, a component precursor molecule to 2-n-butyl-3-fluoropyrroles, was prepared with Cu(0) catalyst. It reacted with various primary amines to yield N-substituted 2-n-butyl-3-fluoropyrroles. The products were synthesized via a one-pot reaction scheme between $\alpha,\alpha-Difluoro-\gamma-iodo-\gamma$-(trimethylsilyl) propyl n-butyl ketone and primary amines in excess ( $\geq$ 5 molar equivalence), which eliminate the need of KF required in obtaining n-butyl-1H-3-fluoropyrrole. The yield of products depended reversely on spatial bulkness around N-binding carbon.

Trimethylsilyl 유도체화 방법을 적용한 함초 추출물의 GC-MS 분석 (GC-MS analysis of Salicornia herbacea L. extracts with trimethylsilyl derivatization)

  • 이경인;이근직;윤영승
    • 한국해양바이오학회지
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    • 제15권2호
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    • pp.96-102
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    • 2023
  • Salicornia herbacea, a noted halophyte, has been widely researched for its diverse physiological activities. The continuous exploration of its compounds is essential. This study employed gas chromatography (GC) coupled with mass spectrometry (MS) for qualitative analysis. This involved pretreatment including trimethylsilyl (TMS) derivatization of the S. herbacea extract, facilitating its GC analysis. Five compounds, including various fatty acids and β-sitosterol, were identified by direct analysis of the methanol extract of S. herbacea without pretreatment by GC-MS. Conversely, the analysis of the TMS-derivatized extract revealed 28 distinct peaks. Quantitative analysis further indicated that the predominant compounds in the S. herbacea extract were sugars and sugar derivatives, notably glucose, fructose, and glucitol. The collective concentration of these sugars and its derivatives amounted to 116.45 mg/g, representing 11.6% of the dry weight of the raw S. herbacea. Following sugars and their derivatives, fatty acids constituted the next most abundant group of compounds. However, the presence of amino acids and organic acids was relatively low.

Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

  • Cho, Dae-Won;Oh, Sun-Wha;Kim, Dong-Uk;Park, Hea-Jung;Xue, Jin-Ying;Yoon, Ung-Chan;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • 제31권9호
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    • pp.2453-2458
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    • 2010
  • Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and $\gamma$-hydrogen abstraction pathways.

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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    • 제26권11호
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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.

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

  • 박근형
    • Applied Biological Chemistry
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    • 제28권2호
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    • pp.82-87
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    • 1985
  • GC-SIM분석법에 의한 GA의 동정 및 정량분석에 대한 정확성과 정출감도의 향상을 목적으로, 29종의 GA를 Me-TMS와 TMS-TMS유도체를 만들고, GC-MS에 의해 이들 유도체의 mass spectra를 측정하였으며, GC-SIM분석에 있어서 Me-TMS유도체와 TMS-TMS유도체의 장단점에 대해 검토하였다.

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