• Title/Summary/Keyword: Tolyl

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Amine and Olefin Complexes of Pt(II) Having a PCP-Pincer Ligand

  • Park, Soon-Heum
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.132-136
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    • 2002
  • $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)\;(OTf=CF_3SO_3^-)$ readily reacts with various amines to afford cationic amine complexes $[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(amine)](OTf)\;(amine=NH_3,\;NHMe_2,\;NHC_4H_8,\;NH_2Ph,\;NH_2(Tol-p))$ in high yields. These complexes have been fully characterized by IR, $^1H-,\;^{19}F{^1H}-,\;and\;^{31}P{^1H}-NMR$ spectroscopy, and elemental analyses. Reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with acrylonitrile quantitatively produced the ${\pi}$-olefinic complex $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)](OTf)$ which is only stable in solution in the presence of acrylonitrile. Attempt at isolating this complex in the pure solid state was failed due to partial decomposition into $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ The equilibrium constants $(K_{eq}=[Pt(PCP)-(NH_2R)^+][CH_2=CHCN]/[Pt(PCP)(CH_2=CHCN)^+][NH_2R]:\;[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)]^++NH_2R{\rightleftarrows}[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(NH_2R)]^++CH_2=CHCN=Ph,\;p-tolyl)$ were calculated to be 0.28 (for R = Ph) and 3.1 (R = p-tolyl) at $21^{\circ}C$. The relative stability of the ${\sigma}$-donor amine versus the ${\pi}$-olefinic acrylonitrile complex has been found largely dependent upon the amine-basicity $(pK_b)$, implicating that acrylonitrile practically competes with amine in the platinum coordination sphere. On the contrary to the formation of the acrylonitrile complex, no reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with other olefins such as ethylene, styrene and methyl acrylate was observed.

전면 발광 유기 발광 소자에서 두께에 따른 발광 스펙트럼 연구

  • Yang, Ji-Won;Han, Won-Geun;Lee, Won-Jae;Lee, Ho-Sik;Kim, Tae-Wan
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2009.11a
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    • pp.20-21
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    • 2009
  • 우리는 전면 발광 소자에서 두께에 따른 발광 스펙트럼을 연구하였다. 소자 구조는 Al(100nm)/TPD(40nm)/Alq3(60nm)/LiF(0.5nm)/Al(2nm)/Ag(30nm)으로 하였다. N,N'-diphenyl-N,N'-di(m-tolyl)-benzidine(TPD)와 tris-(8-hydroxyquinoline) aluminium(Alq3)는 전공 수송층과 발광층으로 각각 사용되었다. 반투명 전극은 Li/Al/Ag로 하였다. 유기물층과 전극은 $2\times10-5$torr의 진공도에서 열 증착하였다. 유기물과 금속의 증착 속도는 $0.5\sim1.0{\AA}/s$$0.5\sim5{\AA}/s$로 하였다. 제작된 소자는 두께가 증가할 수록 장파장으로 이동하는 현상을 보였다. 이러한 현상은 마이크로 캐비티 이론으로 설명할 수 있다. 소자는 이론적인 마이크로 캐비티 수식을 이용하여 분석하기 위해 각각의 변수를 이용하여 실험과 이론을 비교하였을 때, 각각의 스펙트럼이 거의 일치하는 것을 확인할 수 있었다.

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The Study of Photosensitive Polyimide for Organic Electroluminescence (광반응성 폴리이미드를 이용한 유기전기발광소자에 관한 연구)

  • Rho, Sok-Won;Shin, Dong-Myung;Shon, Byoung-Choung
    • Journal of the Korean Applied Science and Technology
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    • v.15 no.4
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    • pp.21-25
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    • 1998
  • Organic-based electroluminescent devices have attracted lots of interests because of their possible application as a large-area flat panel display. Polyimides have been used for photo-alignment in LCD(Liquid Crystal Display). However, the devices used in this study were fabricated with polyimide doped with N,N'-Diphenyl-N,N'-di(m-tolyl)-benzidine(TPD) (3, 10, 30wt%) for electroluminescent hole tranforting layer(EHTL). The photochemical and physical properties of EHTL was studied. The film thicknesses were reduced under illumination with UV light. Polyimide films doped with TPD(3wt%) was irradiated and the electrical properties of the films were studied.

DFT 계산을 이용한 Buchwald-Hartwig amination 반응 메커니즘 연구

  • Gang, Seong-U
    • Proceeding of EDISON Challenge
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    • 2014.03a
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    • pp.371-383
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    • 2014
  • 이 연구에서는 팔라듐 착물 $Pd(PPh_3)_2$을 사용한 bromotoluene과 morpholine간의 coupling reaction (Buchwald-Hartwig amination) 반응 메커니즘을 계산화학적 방법을 이용하여 연구하였다. 용매화 자유에너지를 고려한 중간체 에너지를 비교하였으며, 반응물질이 o-bromotoluene 일 때와 p-bromotoluene 일 때, 반응 중간체로 monophosphine 착물이 형성되는 경우와 bisphosphine 착물이 형성되는 경우를 비교하였으며, 반응 중간체로 bisphosphine 착물이 형성되는 경우 cis 이성질체가 중간체인 경우와 trans 이성질체가 중간체인 경우를 비교하였다. 그 결과, 반응물로 p-bromotoluene을 사용할 때 o-bromotoluene을 사용할 때보다 중간체가 상대적으로 더 안정하여 더 좋은 수득률을 얻을 수 있을 것으로 예상되었다. 또한 $Pd(PPh_3)_n(o-tolyl)(N(CH_2CH_2)_2O)$ (n=1 또는 2) 중간체를 제외하고는 모든 경우에서 bisphosphine 중간체가 형성되는 반응경로가 더 안정한 것으로 밝혀졌다. 그리고 $Pd(PPh_3)_2ArBr$의 경우 trans 이성질체가 cis 이성질체보다 안정하지만 $Pd(PPh_3)_2Ar(N(CH_2CH_2)_2O)$의 경우 반대로 cis 이성질체가 trans 이성질체보다 안정한 것으로 나타났다.

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Synthesis and Reactions of Some Pyridazine Derivatives

  • A, Khalifa-Fathy
    • Archives of Pharmacal Research
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    • v.13 no.2
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    • pp.198-200
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    • 1990
  • 3, 4-Diphenyl-5-cyanopyridazin-6-one 3 was prepared from the reaction of cyano acetamide 2 with benzihydrazone in dry pyridine. A series of its derivatives was prepard. Tolyl and benene sulphonyl derivatives 6a and 6b are also prepared. 3, 4-Diphenyl-5-cyanopyridazin-6-thione 5 was obtained from 3 by the action of $P_2S_5$ while 3, 4 diphenyl-5-cyano 6-chloropyridazine 4 was obtained from 3 by the action POCl$_3$. The reaction of 4 with hydrazine hydrate directly afforded the pyrazolopyridazine derivative 7. Compound 4 also reacted with phenylhydrazine, aniline, thiophenol and anthranilic acid to yield pyridazine derivatives 8, 9, 10 and 11, respectively. On treatment of compound 11 with acetic anhydride it cyclised to afford pyridazino pyrimidine derivatives 12.

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Allylic fluorination

  • Park, Oee-Sook;Son, Hoe-Joo;Lee, Woo-Young
    • Archives of Pharmacal Research
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    • v.10 no.4
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    • pp.239-244
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    • 1987
  • An efficient and inexpensive method for the substitution of allylic hydroxyl group with fluoride, without allylic rearrangement, and elimination was developed. This method consists of treating an allylic alcohol with methylithium, followed by p-toluene sulfonyl fluoride, lithium fluoride and 12-Crown-4. This methodology was proved to be efficient by preparting geranyl fluoride, neryl fluoride, cinnamyl fluoride, E, E-farnesyl fluoride, retinyl fluoride and 4-fluoro-2-methyl-6-(ptolyl)-2-heptene.

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Density Functional Theory Demonstration of Anomeric Effect and Structure: Conformational and Configurational Analysis of N-2-(1,4-Dioxane)-N'-(4-methylbenzenesulfonyl)-O-(4-methylphenoxy) Isourea

  • Dabbagh, Hossein A.;Najafi Chermahini, Ali Reza;Modarresi-Alam, Ali Reza
    • Bulletin of the Korean Chemical Society
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    • v.26 no.8
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    • pp.1229-1234
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    • 2005
  • The conformational, configurtational behavior and the structure of N-2-(1,4-Dioxane)-N'-(4-methylbenzenesulfonyl)-O-(4-methylphenoxy) isourea 1 has been studied using DFT method. Calculations predict the imidoyl amino group of the dioxane ring prefers axial conformation and that the tosyl and tolyl groups about the C=N bond retain E configuration. The anomeric effect controls the population of dioxane ring conformers, and anomers. Intramolecular hydrogen bonds contribute to the stability of E isomers. The computational analysis of 1 complements the X-ray findings.

Benzylic Brominations with N-Bromosuccinimide in 1,2-Dichlorobenzene: Effective Preparation of (2-Bromomethyl-phenyl)-Methoxyiminoacetic Acid Methyl Ester

  • Lee, Sanghyuck;Ra, Choon Sup
    • Clean Technology
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    • v.22 no.4
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    • pp.269-273
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    • 2016
  • The benzylic bromination of methoxyimino-o-tolyl-acetic acid methyl ester (1) into (2-bromomethyl-phenyl)-methoxyimino-acetic acid methyl ester (2) using N-bromosuccinimide in the presence of 2,2'-azobisisobutyronitrile in various reaction solvents were investigated. The efficiency of the reaction was found to be sensitive to the kind of reaction solvents. We found the benzylic bromination of 1 to 2 can be performed in 1,2-dichlorobenzene as reaction solvent superior to the classic Wohl-Ziegler procedure in both reaction time and isolated yield (8 h vs 12 h, 92 vs 79%). This system provides clean, rapid, and high-yielding reactions with replacement of conventional solvents, such as tetrachloromethane, by less-toxic 1,2-dichlorobenzene.

Dehydrogenative Polymerization of New Alkylsilanes Catalyzed by $Cp_2MCl_2$/Red-Al System (M=Ti, Hf)

  • 우희권;김숙연;조은정;정일남
    • Bulletin of the Korean Chemical Society
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    • v.16 no.2
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    • pp.138-143
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    • 1995
  • Substituted 3-phenyl-1-silabutanes, 3-chlorophenyl-1-silabutane (1), 3-tolyl-1-silabutane (2), and 3-phenoxyphenyl-1-silabutane (3), were prepared in 68-98% yield by reduction of the corresponding substituted 3-phenyl-1,1-dichloro-1-silabutanes with LiAlH4. The dehydrogenative homopolymerization and copolymerization of the silanes were performed with Cp2MCl2/Red-Al (M=Ti, Hf) catalyst system. The molecular weights of the resulting polymers were in the of range 600 to 1100 (vs polystyrene) with degree of polymerization (DP) of 5 to 8 and polydispersity index (PDI) of 1.6 to 3.8. The monomer silanes underwent the dehydrogenative polymerization with Cp2TiCl2/Red-Al catalyst to produce somewhat higher molecular weight polysilanes compared with Cp2HfCl2/Red-Al catalyst.

Alkenylation of o-xylene with 1,3-Butadiene Over Base Catalysts (염기성 촉매를 이용한 o-xylene과 1,3-Butadiene의 알케닐화 반응)

  • Lee, Jong Seok;Lee, Soo Chool;Kil, Min Ho;Choi, Il Seok;Lee, Jae Sung;Kim, Jae Chang
    • Korean Chemical Engineering Research
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    • v.40 no.6
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    • pp.669-675
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    • 2002
  • The alkenylation of o-xylene with 1,3-butadiene to make OTP(ortho-tolyl Pentene) was carried out over liquid phase NaK alloy, Na metal and the metallic sodium dispersed on the specific support such as NaX and $Al_2O_3$. Liquid phase NaK alloy showed the improved conversion and selectivity when they were pretreated by ultrasound to increase the dispersion. For the case of metallic sodium, the induction period for the formation of homogeneous metal sodium solution with high dispersion was needed before the reaction. In the case of metallic sodium dispersed on support, more than 80 % conversion could be obtained without induction period regardless of supports used. But 85 % of the metallic sodium was resolved into the reaction mixture after reaction for 7 hours. The amount of byproducts, oligomers, produced from OTP and 1,3-butadiene increased with the amount of 1,3-butadiene introduced and the selectivity to OTP was in inversely proportional to the conversion.