• Title/Summary/Keyword: $S_N2-S_N2'$ Reaction

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Synthesis and Characterization of Homo-, Hetero-Dinuclear Mo(Ⅲ) and V(Ⅲ) Complexes (Ⅳ) (몰리브덴(Ⅲ) 과 바나듐(Ⅲ) 호모 및 헤테로 이핵 착물의 합성과 특성 (제 4 보))

  • O, Sang O;Yu, Eun Yeong
    • Journal of the Korean Chemical Society
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    • v.38 no.11
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    • pp.808-818
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    • 1994
  • The neutral compounds [$MCl_3L_2$(MeCN)] (M = Mo, V: L = $PPh_3$, 1/2 phda) have been prepared from the reaction of starting material $MCl_z$ (M = Mo; z = 5, M = V; z = 3) with N,P-donating ligands in acetonitrile solution. Addition of $AgClO_4$ to these neutral monomeric compounds in acetone solution were produced [$MCl_3-_nL_2(MeCN)(S)_n$]$(ClO_4)_n$ (n = 1, 2 : s = solvent). Finally treatment of bivalent cationic compound and neutral compound was formed chloride bridged dinuclear complex $[(MeCN)(L)_2ClM({\mu}-Cl)_2M'Cl(L)_2(MeCN)](ClO_4)_2$ and treatment of univalent cationic compound with half equivalent pyrazine to pyrazine bridged complex $[(MeCN)(L)_2Cl_2M({\mu}-pyz)M'Cl_2(L)_2(MeCN)](ClO_4)_2$. These complexes are characterized by elemental analysis, $^1H$, $^{13}C$ NMR, IR, Far-IR and UV-Vis spectroscopy.

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Solvolysis of (1S)-(+)-Menthyl Chloroformate in Various Mixed Solvents

  • Koh, Han Joong;Kang, Suk Jin
    • Journal of the Korean Chemical Society
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    • v.65 no.5
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    • pp.309-312
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    • 2021
  • The solvolysis of (1s)-(+)-menthyl chloroformate (1) were studied kinetically in 28 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolysis of 1 obtained the l value of 2.46 ± 0.18, the m value of 0.91 ± 0.07, and the correlation coefficient of 0.950. The solvolysis of 1 might proceed via an associative SN2 mechanism enhancing bond making than bond breaking in the transition state (TS). The value of l/m is 2.7 within the ranges of value found in associative SN2 reaction. This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.16).

Regioselective Synthesis of Heterocyclic Ketene N,N-, N,O- and N,S-acetals in Aqueous Medium

  • Chanu, Langpoklakpam Gellina;Singh, Okram Mukherjee;Jang, Sang-Hun;Lee, Sang-Gyeong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.859-862
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    • 2010
  • The reactions of ketene dithioacetals with ethane-1,2-diamine, propane-1,3-diamine, 2-aminoethanol, 3-aminopropanol, and 2-aminoethanethiol in ordinary water in the absence of any acid/base catalyst afforded the heterocyclic ketene N,N-, N,O- and N,S-acetals in good yields.

Brazing of Aluminium Nitride(AlN) to Copper with Ag-based Active Filler Metals (은(Ag)계 활성금속을 사용한 질화 알미늄(AlN)과 Cu의 브레이징)

  • Huh, D.;Kim, D.H.;Chun, B.S.
    • Journal of Welding and Joining
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    • v.13 no.3
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    • pp.134-146
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    • 1995
  • Aluminium nitride(AlN) is currently under investigation as potential candidate for replacing alumium oxide(Al$_{2}$ $O_{3}$) as a substrate material for for electronic circuit packaging. Brazing of aluminium nitride(AlN) to Cu with Ag base active alloy containing Ti has been investigated in vacuum. Binary Ag$_{98}$ $Ti_{2}$(AT) and ternary At-1wt.%Al(ATA), AT-1wt.%Ni(ATN), AT-1wt.% Mn(ATM) alloys showed good wettability to AlN and led to the development of strong bond between brate alloy and AlN ceramic. The reaction between AlN and the melted brazing alloys resulted in the formation of continuous TiN layers at the AlN side iterface. This reaction layer was found to increase by increase by increasing brazing time and temperature for all filler metals. The bond strength, measured by 4-point bend test, was increased with bonding temperature and showed maximum value and then decreased with temperature. It might be concluded that optimum thickness of the reaction layer was existed for maximum bond strength. The joint brazed at 900.deg.C for 1800sec using binary AT alloy fractured at the maximum load of 35kgf which is the highest value measured in this work. The failure of this joint was initiated at the interface between AlN and TiN layer and then proceeded alternately through the interior of the reaction layer and AlN ceramic itself.

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Processing and Thermal Properties of S${i_3}{N_4}$-BN Composites (S${i_3}{N_4}$-BN복합재료의 제조 및 열적 특성)

  • Lee, O-Sang;Park, Hui-Dong;Lee, Jae-Do
    • Korean Journal of Materials Research
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    • v.3 no.4
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    • pp.381-387
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    • 1993
  • The silicon oxynitride bonded $Si_3N_4-BN$ composite has been developed based on the selective oxidation behavier of $Si_3N_4$ over BN. The silicon oxynitride phase converted to the reaction between $Si_3N_4$ and $SiO_2$ formed on $Si_3N_4$ powder surface during oxidation treatment at the sintering temperature. The developed composite has excellent high-temperature strength, thermal shock resistance, precision machinability and corrosion resistance to the molten steel. The developed composite may therefore be used as, for example, break ring materials in continuous casting of steel.

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Synthesis and Characterization of Dinuclear Mo(Ⅲ) and V(Ⅲ) Complexes (Ⅴ) (몰리브덴(Ⅲ)과 바나듐(Ⅲ) 이핵 착물의 합성과 특성 (제5보))

  • Oh, Sang-Oh;Lyou, Eun-Young
    • Journal of the Korean Chemical Society
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    • v.39 no.7
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    • pp.530-537
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    • 1995
  • The neutral complexes $MCl_3(phda)(MeCN)]$ and $[MCl_3(PPh_3)_2(MeCN)]$ (M=Mo, V) were prepared by the reaction of $MCl_z$, (M=Mo; z=5, M=V; z=3) with N, P-donating ligands in acetonitrile solution. Addition of AgClO_4$ to these neutral monomeric complexes in acetone solution afforded $MCl_{3-n}L_2(MeCN)(S)_n](ClO_4)_n$ (n=1, 2 : s=solvent). Two types of asymmetrical homo- and hetero-dinuclear complexes have been synthesized. The type of chloride bridged dinuclear complex is $[(MeCN)(phda)ClM({\mu}-Cl)_2M'Cl(PPh_3)_2(MeCN)](ClO_4)_2.$ And the type of pyrazine bridged complex is $[(MeCN)(phda)Cl_2M({\mu}-pyz)M'Cl_2(PPh_3)_2(MeCN)](ClO_4)_2.$ These complexes were characterized by elemental analysis, $^1H,\;^13C$ NMR, IR, Far-IR and UV-Vis spectroscopy.

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Preparation of Poly(imide-aramid-sulfone)s and their Thermal Properties (폴리(이미드-아라미드-설폰)의 합성과 그들의 열적성질)

  • Park, Hyung-Seok;Gong, Myoung-Seon
    • Polymer(Korea)
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    • v.36 no.4
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    • pp.427-433
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    • 2012
  • A series of poly(imide-aramid-sulfone)s with alternatingly introduced imide/aramid groups were prepared by reacting divinyl sulfone (DVS) and $N^1,N^4$-bis(4-(vinylsulfonyl)phenyl)terephthalamide (2) with pyromellitic diimide. Three model compounds, N-[2-(p-aminophnenylsulfonyl)ethyl]phthalimide (3), 2,2'-(2,2'-sulfonylbis(ethane-2,1-diyl))diisoindoline-1,3-dione (4), and N,N-bis(4-(2-(1,3-dioxoisoindolin-2-yl)ethylsulfonyl)phenyl)terephthalamide (5), resembling polymers were prepared with good yields by reacting p-aminophenyl vinyl sulfone, DVS, and 2 with phthalimide. Condensation polymerization was carried out by Michael-type addition reaction of the difunctional phthalimide group with the DVS group in the presence of tetrabutylammonium hydroxide (TBAH), resulting in poly(imide-aramid-sulfone)s 6-12 with moderate molecular weights and good yields. They were highly soluble in polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone and tetrahydrofuran. The ratios of DVS/2 were 1/0, 3/1, 2/1, 1/1, 1/2, 1/3, and 0/1. Molecular weight and physical properties such as solubility, viscosity, and thermal properties of the polymers were examined.

Molecular Switching Coordination Polymers. 4.4'-Chalcogenobispyridine Bridged Cobalt Benzoquinone Complexes

  • 조두환;정종화;여환진;손윤수;정옥상
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.504-507
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    • 1995
  • The reaction of Co2(CO)8 with 3,6-di-tert-butyl-1,2-benzoquinone in the presence of the respective 4,4'-chalcogenobispyridine results in the coordination polymers of [CoⅢ(4,4'-X(Py)2)(DBSQ)(DBCat)]n (X=S, Se, Te; Py=pyridine; DBSQ=3,6-di-tert-butylsemiquinone; DBCat=3,6-di-tert-butylcatechol). The title compounds undergo an intramolecular Cat → Co electron transfer, and thus change toward the [CoⅡ(4,4'-X(Py)2)(DBSQ)2]n at elevated temperature. The temperature-switching properties of the compounds directly depend upon the electronegativity of the chalcogen atom of the 4,4'-chalcogenobispyridine coligands. The spectroscopic data disclose that the properties of [CoⅢ(4,4'-S(Py)2)(DBSQ)(DBCat)]n and [CoⅢ(4,4'-Se(Py)2)(DBSQ)(DBCat)]n are similar each other in contrast to those of [CoⅢ(4,4'-Te(Py)2)(DBSQ)(DBCat)]n.

Kinetics and Mechanism of the Anilinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4361-4365
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    • 2011
  • The nucleophilic substitution reactions of bis(N,N-dimethylamino) phosphinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The magnitudes of ${\rho}_X$ (= -6.42) and ${\beta}_X$ (= 2.27) values are exceptionally great. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.69-0.96). A concerted $S_N2$ mechanism involving a backside attack is proposed on the basis of secondary inverse DKIEs and the variation trend of the $k_H/k_D$ values with X. The anilinolyses of six phosphinic chlorides in MeCN are briefly reviewed by means of DKIEs, steric effects of the two ligands, positive charge of the reaction center phosphorus atom, and selectivity parameters to obtain systematic information on phosphoryl transfer reaction mechanism.

Adsorption Selectivities between Hydroxypyridine and Pyridone Adsorbed on the Ge(100) Surface

  • Lee, Myungjin;Lee, Hangil
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.137-137
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    • 2013
  • The most stable adsorption structures and their corresponding energies of 4-pyridone, 4-hydroxypyridine, 2-pyridone and 2-hydroxypyridine have been investigated by Density Functional Theory (DFT) calculation method and high-resolution photoemission spectroscopy (HRPES). We confirmed that between the two reaction centers of 4- and 2-pyridone, only O atom of carbonyl functional group can act as a Lewis base and thus, O dative bonding structure is the most stable. On the other hand, we clarified that both the two reaction centers (the cyclic N atom and the O atom of hydroxyl functional group) of 4- and 2-hydroxypyridine (tautomers of 4- and 2-pyridone) can successfully function as a Lewis base. Through the interpretation of the N 1s and O 1s core level spectra obtained using HRPES, we could confirm the electronic structures and bonding configurations of these molecules with a coverage dependence on the Ge(100) surface.

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