• Title/Summary/Keyword: C-H Functionalization

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Transition Metal-Catalyzed Ortho-Functionalization in Organic Synthesis

  • Park, Young-Jun;Jun, Chul-ho
    • Bulletin of the Korean Chemical Society
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    • v.26 no.6
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    • pp.871-877
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    • 2005
  • Recent progress in the filed of transition-metal mediated C-H bond activation has had a great influence on organic synthesis. Among such transition-metal catalyzed reactions, ortho-functionalization via the chelationassisted strategy has been paid great attentions as one of the powerful methodologies for converting aromatic compounds into ones that are more functionalized at the exclusively ortho-position. In this context, various transition metal-catalyzed ortho-functionalizations such as alkylation, alkenylation, silylation and carbonylation are described briefly and their prospects are suggested.

Anionic Synthesis of Dipyridine Chain End-Functionalized Polystyrene and Polybutadiene (리빙 음이온 중합에 의한 Dipyridine 말단 관능화 폴리스티렌 및 폴리부타디엔의 합성)

  • Ji, Sang-Chul;Lee, Jong-Seop;Kim, Doo-Hwan;Kang, Cheol-Han;Park, Jong-Hyuk;Lee, Bum-Jae
    • Polymer(Korea)
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    • v.34 no.2
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    • pp.159-165
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    • 2010
  • Dipyridine-terminated polystyrenes and polybutadienes were synthesized by the chain endfunctionalization reaction of polystyryllithium (PSLi) and polybutadienyllithium (PBDLi) with di(2-pyridyl) ketone(DPK) using a living anionic polymerization method in the Ar-glove box. Living polymeric lithiums with low molecular weights (Mw=1000~2000 g/mol) were used to investigate the chain end-functionalization yield with DPK and the degree of coupling reaction by the attack of organolithium to the pyridine ring in the presence of TMEDA using GPC, $^1H$-NMR, $^{13}C$ analysis. DPK-terminated PBD exhibited much higher functionalization yield and less amount of coupling reaction compared with DPK-terminated PS. 86% functionalization yield with 9% degree of coupling was obtained when the PBDLi was added dropwise to DPK solution at room temperature. The functionalization yield was increased as the reaction temperature decreased, however, no LiCl effect was observed in this chain end-functionalization reaction with DPK.

Carbon Nano-Powder Functionalization and Disperisibility with Plasma Discharge

  • Gang, Yu-Seok;Jeong, Man-Gi;Lee, Deok-Yeon;Song, Seok-Gyun;Kim, Seong-In
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.491-491
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    • 2013
  • A novel plasma system has been developed for 3-dimensional modification of the carbon nano-powders. Improvement of dispersion of these nano materials are studied by plasma discharge, not using chemical modification. The plasma process is considered to great advantages over wet chemical process due to environmental, economic viewpoint, and uniformity over the treated volume. The uniform dispersion is a critical factor for these material's nano composite applications. Using this plasma system, graphene, carbon black, and CNT was treated and functionalized. Several key discharge conditions such as Ar/H2/O2 or Ar/H2/NH3 gas ratio, treatment time, power, feeder's vibration frequency are investigated. Hydrophobic of graphene has turned some more into hydrophilic by reaction test with water, electrophoresis, surface contact angle test, and turbidity analysis. The oxygen content ratio in the plasma treated CNT has increased about 3.7 times than the untreatedone. In the case of graphene and carbon black, the oxygen- and nitrogen- content has been enhanced average 10%. O-H (N-H) peak, C-O (C-N) peak, and C=O (C=N) peak data have been detected by FTIR measurement and intensified compared to before-plasma treatment due to O2 or NH3 content.

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Functionalization of Wool Fiber Using Water-Soluble C-60 (수용성 C-60을 이용한 양모섬유의 기능화)

  • Jeon, Yeong-Sil;Gwon, Hyeok-Seong;Nam, Seong-U;Kim, In-Hoe
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2008.04a
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    • pp.77-79
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    • 2008
  • Polynitro fullerenes were synthesized by reaction C-60 in benzen solution with a mixture of NaNO$_2$ and HNO$_3$. Hydrolysis of polynitro fullerenes in aqueous NaOH gave the corresponding polyhydroxylated fullerenes. Sulfonation reaction was carried out in pyridine solution of ClSO$_3$H. Infrared spectra of the resultant fullerene derivatives showed the characteristic IR bands, corresponding to absorptions of O-H, N-O, and SO$_3$Na functions. Electric resistivity and thermal transmittance of wool fiber absorbed with the water-soluble C-60 were investigated. Thermal transmittances of wool fiber were increased with increasing water-soluble C-60 concentrations, but electric conductivity were decreased with raising water-soluble C-60 uptake values.

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Aldol Condensation over Acid-Base Bifunctional Metal-Organic Framework Catalysts (산, 염기 이원기능 금속-유기 구조체 촉매를 이용한 알돌 축합반응)

  • Chung, Young-Min
    • Clean Technology
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    • v.20 no.2
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    • pp.116-122
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    • 2014
  • Various types of MOFs (metal-organic frameworks) were prepared via hydrothermal and post-grafting methods and applied as catalysts for the synthesis of jasminaldehyde, one of the representative perfume intermediates, by Aldol condensation of benzaldehyde with heptanal. Although both acid and base sites could catalyze the reaction, the catalytic performance was strongly dependent on the physical properties as well as the nature of functionalization on MOFs. While the use of sulfonated MOF catalysts led to decrease of jasminaldehyde selectivity regardless of MOFs used, the selectivity change was found to rely on the MOF types in the case of the amine-functionalization. Among the catalysts tested, MIL-101 shows the best catalytic performance, which may suggest that MIL-101 has suitable acid properties to promote the Aldol condensation and the large pore of MIL-101 is also advantageous to alleviate the diffusion problem of bulky products.

Ring Formation of Furan on Epitaxial Graphene

  • Kim, Ki-Jeong;Yang, Sena;Lee, Han-Koo;Kim, Bong-Soo;Lee, Hang-Il
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.315-315
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    • 2011
  • The ring formation and electronic properties of furan adsorbed on graphene layers grown on 6H-SiC(0001) has been investigated using atomic force microscopy (AFM), near edge X-ray absorption fine structure (NEXAFS) spectra for the C K-edge, and high resolution photoemission spectroscopy (HRPES). Moreover, we observed that furan molecules adsorbed on graphene could be used for chemical functionalization via the lone pair of electrons on the oxygen group, allowing chemical doping. We also found that furan spontaneously formed rings with one of three different bonding configurations and the electronic properties of the ring formed by furan on graphene can be described using by AFM, NEXAFS and HRPES, respectively.

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Multinuclear Solid-state NMR Investigation of Nanoporous Silica Prepared by Sol-gel Polymerization Using Sodium Silicate

  • Kim, Sun-Ha;Han, Oc-Hee;Kim, Jong-Kil;Lee, Kwang-Ho
    • Bulletin of the Korean Chemical Society
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    • v.32 no.10
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    • pp.3644-3649
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    • 2011
  • Multinuclear solid-state nuclear magnetic resonance (NMR) experiments were performed to investigate the local structure changes of nanoporous silica during hydrothermal treatment and surface modification with 3-aminopropyltriethoxysilane (3-APTES). The nanoporous silica was prepared by sol-gel polymerization using inexpensive sodium silicate as a silica precursor. Using $^1H$ magic angle spinning (MAS) NMR spectra, the hydroxyl groups, which play an important role in surface reactions, were probed. Various silicon sites such as $Q^2$, $Q^3$, $Q^4$, $T^2$, and $T^3$ were identified with $^{29}Si$ cross polarization (CP) MAS NMR spectra and quantified with $^{29}Si$ MAS NMR spectra. The results indicated that about 25% of the silica surface was modified. $^1H$ and $^{29}Si$ NMR data proved that the hydrothermal treatment induced dehydration and dehyroxylation. The $^{13}C$ CP MAS and $^1H$ MAS NMR spectra of 3-APTES attached on the surface of nanoporous silica revealed that the amines of the 3-aminopropyl groups were in the chemical state of ${NH_3}^+$ rather than $NH_2$.

Study on Poly(triazine bissulfide)s Derivatives being the Synthesized Optical Plastic Material (합성한 광학플라스틱 재료인 Poly(triazine bissulfide)s 유도체에 대한 연구)

  • Lee, Y.H.;Lee, D.H.;Kim, J.J.;Ha, T.W.;Cha, J.W.
    • Journal of Korean Ophthalmic Optics Society
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    • v.9 no.2
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    • pp.481-489
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    • 2004
  • Poly(triazine bissulfide)s were synthesized from 6-dibutylamino-1,3,5-triazine-2,4-dithiol with bis(4-chloro-3-nitrophenyl)sulfone in the presence of the phase transfer catalyst, and from m-dibromide xylene and p-dibromide xylene with 6-dibutylamino-1,3,5-triazine-2,4-dithiol in the presence of cetyltrimethyl ammonium bromide at $70^{\circ}C$ for 24h. We could acquire the good results about solubility, thermal property, and molecular weight to make cast film. These results are important as base for the synthesis of functionalization polymer material being optical plastic material. The maximum algebra viscosity was 0.57~1.40dl/g at the temperature more than $50{\sim}60^{\circ}C$.

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