• Title/Summary/Keyword: C-C Bond formation

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Synthesis and Potent Anti-leukemic Activity of Novel 5'-Norcarbocyclic C-nucleoside Phosphonic Acids

  • Kim, Seyeon;Kim, Eunae;Oh, Chang-Hyun;Yoo, Kyung Ho;Hong, Joon Hee
    • Bulletin of the Korean Chemical Society
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    • v.35 no.12
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    • pp.3502-3508
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    • 2014
  • The first synthetic route to 5'-norcarbocyclic C-nucleoside [7-oxa-7,9-dideazadenosine (furo[3,2-d]pyrimidine) and 9-deazaadenosine (pyrrolo[3,2-d]pyrimidine)] phosphonic acids from commercially available 1,3-dihydroxy cyclopentane was described. The key C-C bond formation from sugar to base precursor was performed using Knoevenagel-type condensation from a ketone derivative. Synthesized C-nucleoside phosphonic acids were tested for anti-HIV activity as well as anti-leukemic activity. Compound 26 showed significant anti-leukemic activity.

Mass Spectrometry of Dammarane Triterpenoids (Dammarane계(係) Triterpenoid의 질량분광분석(質量分光分析))

  • Han, Byung-Hoon;Kim, Jae-Hoon;Chi, Hyung-Joon
    • Korean Journal of Pharmacognosy
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    • v.10 no.2
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    • pp.55-59
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    • 1979
  • Mass spectra of the dammarane triterpenes having open side chain and $C_{20}-C_{25}-epoxy$ side chain were measured. Principal fragment ions were assigned and plausible mechanisms for the formation of the fragment ions were proposed. In general, the triter-penoids of $C_{20}-C_{25}-epoxy$ side chain. produce $h_{1}-species$ fragment ions by the deletion of side chain at $C_{20}-C_{22}$ bond and open side chain triterpenoids produce $h_{2}$ species fragmentions whose mass numbers are higher by two mass unit than those of $h_{1}$ species. The mass number of h species fragment ions will serve as the diagnostic tool for the elucidation of side chain structure of tetracyclic triterpenoids.

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Synthesis of N-Aryl Phenylglycine Ο-Alkyl Esters and Its Substitution of Ester Moiety (N-Aryl Phenylglycine Ο-Alkyl Esters의 간편한 합성 및 에스테르 치환반응)

  • 박명숙;박해선
    • YAKHAK HOEJI
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    • v.47 no.5
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    • pp.276-282
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    • 2003
  • For the development of new synthetic method for unnatural amino acid esters, N-aryl phenylglycine Ο-alkyl esters 4a∼i were synthesized through esterification, bromination, C-N bond formation from commercially available phenylacetic acids. An efficient and practical reaction condition for esters 2a∼c was that the starting materials 1a∼c were refluxed in absolute methanol for 3 hours with catalytic concentrated hydrosulfuric acid. In addition, bromines 3a∼c were formated for 3h in dichloromethane at rt with N-bromosuccinimide. Bromines 3a∼c were also converted to 4a∼i through substitution of arylamines during refluxing for 24 hours in ethanol with triethylamine. Interestingly, ethyl esters 5a∼c were formed via transesterification reaction when the p-sulfamylanilino group was used as a nucleophile in ethanol solvent.

Intramolecular Ion-Molecule Reactions within Ti+(CH3COCH3)n Heteroclusters: Oxidation Pathway via C=O Bond Activation

  • Koo, Young-Mi;Hong, Ki-Ryong;Kim, Tae-Kyu;Jung, Kwang-Woo
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.953-958
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    • 2010
  • A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within $Ti^+(CH_3COCH_3)_n$ heterocluster ions. The reactions of $Ti^+$ with $CH_3COCH_3$ clusters were found to be dominated exclusively by an oxidation reaction, which produced $TiO^+(CH_3COCH_3)_n$ clusters. These ions were attributed to the insertion of a $Ti^+$ ion into the C=O bond of the acetone molecule within the heteroclusters, followed by $C_3H_6$ elimination. The mass spectra also indicated the formation of minor sequences of heterocluster ions with the formulas $Ti^+(C_3H_4O)(CH_3COCH_3)_n$ and $TiO^+(OH)(CH_3COCH_3)_n$, which could be attributed to C-H bond insertion followed by $H_2$ elimination and to the sequential OH abstraction by the $TiO^+$ ion, respectively. Density functional theory calculations were carried out to model the structures and binding energies of both the association complexes and the relevant reaction products. The reaction pathways and energetics of the $TiO^+\;+\;CH_2CHCH_3$ product channel are presented.

Development of fluorination methodology for carbon-fluorine bond formation: nucleophilic fluorinating reagents in the mid-2000s

  • Bae, Dae Young;Lee, Eunsung
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.3 no.2
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    • pp.129-133
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    • 2017
  • Since carbon-fluorine (C-F) bonds play a key role to improve bioavailability and lipophilicity, they have found commonly in pharmaceuticals, radiopharmaceuticals, agrochemicals, and material science. Advances on the efficient method to introduce fluorine to complex organic molecules are mainly results of development of fluorination reagents and transition metal catalysts. In this mini-review, we want to emphasize two representative nucleophilic fluorinating reagents regarding carbon-fluorine bond formation, which were developed in the mid-2000s.

The Effects of Precursor on the Formation and Their Properties of Spin-on Dielectric Films Used for Sub-50 nm Technology and Beyond (50 nm 이상의 CMOS 기술에 이용되는 Spin-on Dielectric 박막 형성과 그 특성에 미치는 전구체의 영향)

  • Lee, Wan-Gyu
    • Journal of the Korean Vacuum Society
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    • v.20 no.3
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    • pp.182-188
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    • 2011
  • Polysilazane and polymethylsilazane based precursor films were deposited on Si-substrate by spin-coating, subsequently annealed at $150{\sim}850^{\circ}C$, and characterized. Structural analysis, shrink, compositional change, etch rate, and gap-filling were observed. Annealing the precursor films led to formation of spin-on dielectric films. C-containing precursor films showed that less loss of N, H, and C while less gain of O than that of C-free precursor films at $400^{\circ}C$, but more loss of N, H, and C while more gain of O at $850^{\circ}C$. Thus polysilazane based precursor films exhibited less reduction in thickness of 14.5% than silazane based one of 15.6% at $400^{\circ}C$ but more 37.4% than 19.4% at $850^{\circ}C$. FTIR indicated that C induced smaller amount of Si-O bond, non-uniform property, and lower resistance to chemical etching.

Effect of Number and Location of Amine Groups on the Thermodynamic Parameters on the Acridine Derivatives to DNA

  • Kwon, Ji Hye;Park, Hee-Jin;Chitrapriya, Nataraj;Han, Sung Wook;Lee, Gil Jun;Lee, Dong Jin;Cho, Tae-Sub
    • Bulletin of the Korean Chemical Society
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    • v.34 no.3
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    • pp.810-814
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    • 2013
  • The thermodynamic parameters for the intercalative interaction of structurally related well known intercalators, 9-aminoacridine (9AA) and proflavine (PF) were determined by means of fluorescence quenching study. The fluorescence intensity of 9AA decreased upon intercalation to DNA, poly[$d(A-T)_2$] and poly[$d(G-C)_2$]. A van't Hoff plot was constructed from the temperature-dependence of slope of the ratio of the fluorophore in the absence and presence of a quencher molecule with respect to the quencher concentration, which is known as a Stern-Volmer plot. Consequently, the thermodynamic parameters, enthalpy and entropy change, for complex formation was calculated from the slope and y-intercept of the van't Hoff plot. The detailed thermodynamic profile has been elucidated the exothermic nature of complex formation. The complex formation of 9AA with DNA, poly[$d(A-T)_2$] and poly[$d(G-C)_2$] was energetically favorable with a similar negative Gibb's free energy. On the other hand, the entropy change appeared to be unfavorable for 9AA-poly[$d(G-C)_2$] complex formation, which was in contrast to that observed with native DNA and poly[$d(A-T)_2$] cases. The equilibrium constant for the intercalation of PF to poly[$d(G-C)_2$] was larger than that to DNA, and was the largest among sets tested despite the most unfavorable entropy change, which was compensated for by the largest favorable enthalpy. The favorable hydrogen bond contribution to the formation of the complexes was revealed from the analyzed thermodynamic data.

Effect of Pt on the High Temperature Stability of NiCoCrAlY or NiAl Bond Coat in the Thermal Barrier Coating System (NiCoCrAlY 및 NiAl bond coat를 사용한 Thermal Barrier Coating의 고온안정성에 미치는 Pt의 영향)

  • Ku Seongmo;Kim Gil Moo
    • Korean Journal of Materials Research
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    • v.15 no.6
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    • pp.375-381
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    • 2005
  • High temperature oxidation behavior of thermal barrier coating (TBC) system (IN738 substrate + NiCoCrAlY or NiAl bond coat with or without Pt + yttria stabilized zirconia) prepared by air plasma spray (APS) process has been studied in order to understand the effect of Pt addition to bond coat on the stability of TBC system. Specimens were oxidized in thermal cycling and isothermal oxidation test at $1100^{\circ}C$. The Pt addition in TBC system with NiCoCrAlY bond coat showed a longer life time compared to that without addition of Pt. Pt addition to TBC system is believed to help the formation of more stable thermally grown oxide, $Al_2O_3$, at the TBC/bond coat interface, leading to a longer lifetime of TBC system.

Aromatic Formation from Vinyl Radical and Acetylene. A Mechanistic Study

  • Natalia, Debby;Indarto, Antonius
    • Bulletin of the Korean Chemical Society
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    • v.29 no.2
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    • pp.319-322
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    • 2008
  • The viability of acetylene addition in each step of aromatic formation initiated by vinyl radical and acetylene also with its competition with structure rearrangement is investigated by determining optimal geometries and barrier and reaction energies using quantum mechanical methods. In principle, the addition reaction has more difficult in term of free energy and enthalpy compared to geometry arrangement. Under combustion conditions, i.e. T = 1200 K, acetylene addition is unfavorable mechanism as the barrier energy values rise much higher than that of geometry arrangement. However, in longer chain hydrocarbon case, e.g. n-CxHx+1 where x ³ 8, C-C bond rotation is rather difficult and requires high energy to form a ring structure, elongation chain is preferable.

The Dependence of Mechanical Strain on a-Si:H TFTs and Metal Connection Fabricated on Flexible Substrate

  • Lee, M.H.;Ho, K.Y.;Chen, P.C.;Cheng, C.C;Yeh, Y.H.
    • 한국정보디스플레이학회:학술대회논문집
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    • 2006.08a
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    • pp.439-442
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    • 2006
  • We evaluated a-Si:H TFTs fabricated on polyimide substrate (PI) at the highest temperature of $160^{\circ}C$ with uniaxial and tensile strain to imitate flexible display. With tensile strain, the threshold voltage of a-Si:H TFTs have positive shift due to extra dangling bond formation in a-Si:H layer. However, no significant degradation of the subthreshold swing and effective mobility with tensile strain of a-Si:H TFTs indicates the similar level of band tail state. The metal wire with the width of $10\;{\mu}m$ for connection on flexible substrate can sustain with curvature radius 2.5 cm.

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