• Title/Summary/Keyword: Methyl Cyanide

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Three Cyanide-Bridged One-Dimensional Single Chain CoIII-MnII Complexes: Rational Design, Synthesis, Crystal Structures and Magnetic Properties

  • Zhang, Daopeng;Zhao, Zengdian;Wang, Ping;Chen, Xia
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1581-1585
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    • 2012
  • Two pyridinecarboxamide dicyanidecobalt(III) building blocks and two mononuclear seven-coordinated macrocycle manganese(II) compounds have been rationally selected to assemble cyanide-bridged heterobimetallic complexes, resulting in three cyanide-bridged $Co^{III}-Mn^{II}$ complexes. Single X-ray diffraction analysis show that these complexes $\{[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}CH_3OH{\cdot}0.5H_2O$ ($\mathbf{1}$), $\{[Mn(L^2)][Co(bpb)]\}ClO_4{\cdot}0.5CH_3OH$ ($\mathbf{2}$) and ${[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}H_2O$ ($\mathbf{3}$) ($L^1$ = 3,6-diazaoctane-1,8-diamine, $L^2$ = 3,6-dioxaoctano-1,8-diamine; $bpb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate) all present predictable one-dimensional single chain structures. The molecular structures of these one-dimensional complexes consists of alternating units of $[Mn(L)]^{2+}$ ($L=L^1$ or $L^2$) and $[Co(L^{\prime})(CN)2]^-$ ($L^{\prime}=bpb2^{2-}$, or $bpmb2^{2-}$), forming a cyanide-bridged cationic polymeric chain with free $ClO_4{^-}$ as the balance anion. The coordination geometry of manganese(II) ion in the three one-dimensional complexes is a slightly distorted pentagonal-bipyrimidal with two cyanide nitrogen atoms at the trans positions and $N_5$ or $N_3O_2$ coordinating mode at the equatorial plane from ligand $L^1$ or $L^2$. Investigation over magnetic properties of these complexes reveals that the very weak magnetic coupling between neighboring Mn(II) ions connected by the diamagnetic dicyanidecobalt(III) building block. A best-fit to the magnetic susceptibility of complex ${\mathbf}{1}$ leads to the magnetic coupling constants $J=-0.084(3)cm^{-1}$.

Synthesis of Some Heterocycles of Potential Biological Activity

  • Ali-Harb, Abd-Elfattah;Mostafa, Fatma-H.;Metwally, Saoud-A.
    • Archives of Pharmacal Research
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    • v.13 no.2
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    • pp.187-191
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    • 1990
  • A convenient method for the preparation of imidazobenzimidazole 3, imidazoimidazole 5, imidazotriazole 6 and pyrano [2, 3-c] oxazole 7 derivatives is described. This depends on interaction of 2-methyl-4-arylidene-2-oxazolin-5-ones 1 with o-diamines, thiosemicarbazide and/or ethylcyanoacetate. The effect of alcoholic potassium cyanide on axazolinone 1 was studied. Antibacterial activity of the obtained products was studied.

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Preparation of α-Linked 6-Deoxy-D-altro-heptopyranosidic Residues

  • 신영숙;천근호;Shin, E. Nam;Gerald O. Aspinall
    • Bulletin of the Korean Chemical Society
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    • v.16 no.7
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    • pp.625-630
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    • 1995
  • α-Linked D-altropyranosidic derivatives were obtained by configurational change at C-3 of α-D-mannopyranosides as the key step in preparation of allyl and methyl α-D-glycopyranosides of 6-deoxy-D-altro-heptose. The manno-altro conversion was effected by sequential reactions of Swern oxidation and stereoselective borohydride reduction. Allyl 4,6-O-benzylidene-2-O-p-methoxybenzyl-α-D-mannopyranoside was transformed to the corresponding altropyranoside via 3-oxo-arabino-hexopyranoside. Allyl 7-O-benzyl-6-deoxy-3,4-O-isopropylidene-α-D-altro-heptopyranoside has been prepared as a glycosyl acceptor to be coupled with β-D-GlcpNAc-(1→3)-α-D-Galp glycosyl donor for the synthesis of an O-antigen repeating unit of Campylobacter jejuni serotypes O:23 and O:36. Stereoselective borohydride reduction also succeeded in yielding methyl 2,4,7-tri-O-benzyl-6-deoxy-α-D-altro-heptopyranoside from the corresponding 3-oxo-α-D-arabino-heptopyranoside. C-6 Homologation was achieved by sequential reactions of cyanide displacement of 6-sulphonates, reduction of the resulting heptopyranosidurononitrile with diisobutylaluminum hydride, hydrolysis of the imine, and further reduction with sodium borohydride.

Improvement of the Synthetic Route for Epinastine Antihistamine (에피나스틴 항히스타민제의 합성법 개선)

  • Baek, Du-Jong;Kim, Moon-Sik
    • Journal of the Korean Chemical Society
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    • v.54 no.4
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    • pp.447-450
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    • 2010
  • In this study, the improved large-scale synthetic route for epinastine hydrochloride, the second-generation antihistamine, was developed. The original synthetic route involves the synthesis of an aminomethyl derivative, the main intermediate, and in this process hazardous materials such as very toxic phosgene and sodium cyanide along with the explosive and expensive aluminum chloride and lithium aluminum hydride were used. In order to improve the synthetic route, we developed industrially very useful process to prepare the aminomethyl intermediate by the synthesis of the phthalimidomethyl derivative first and easy removal of the phthalyl group using hydrochloric acid or methyl hydrazine, and hazardous materials and expensive reagents were excluded in this process.

Nonlinear Dielectric Properties of VDCN Copolymers (VDCN계 공중합체의 비선형 유전 특성)

  • Gang, Dae-Ha;Park, Sang-Ho
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.51 no.7
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    • pp.279-286
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    • 2002
  • Linear and nonlinear complex permittivities were measured for copolymers of vinylidene cyanide(VDCN) with vinyl acetate(VAc), vinyl propionate(VPr), vinyl bezoate(VBz), styrene(St) and methyl methacrylate(MMA). Experimental results are well fitted by the function (equation omitted) except at low frequency where dc conduction dominates. The analysis of dielectric relaxation mechanism by combined knowledge about linear and nonlinear dielectric permittivities and dipoles give us informations about electrical and thermal motions in these copolymers. According to the analysis it could be found that the variation for temperature of the dielectric relaxation strength in these copolymers is related to the interaction between dipoles and the nonlinear dielectric effect factor R$_{s}$ is proportional to square of the dipolar correlation factor R$_{p}$././.

Quantitative Determination of Acetone formed in the Thermal and Photochemical Decompositions of Azobisisobutyronitrile

  • Yoon, Heung-Sick;Kim ,Kyong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.284-287
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    • 1985
  • Cyanoisopropyl radical derived from azobisisobutyronitrile (AIBN) by either thermolysis or photolysis reacts with oxygen to give cyanoisopropylperoxy radical which then was converted to acetone and cyano radical and/or acetyl cyanide and methyl radical. Of these products, acetone formed was quantitatively determined by the addition of thianthrene cation radical perchlorate to the reaction mixture. The results showed that 55.7 mmol, 16.9 mmol, and 16.0 mmol of acetone were formed for 7 hours from 1 mol of AIBN at $82{\pm}1^{\circ}C$ in acetonitrile, carbon tetrachloride, and benzene, respectively. However, 22.2 mmol of acetone was formed from photolysis of 1 mmol of AIBN in acetonitrile. The value decreased to 13.2 mmol by bubbling argon into the solvent prior to photolysis.

A Study on the Volatile Flavor Components in Kimchis (김치의 휘발성(揮發性) 향미성분(香味成分)에 관(關)한 연구(硏究))

  • Yoon, Jin-Sook;Rhee, Hei-Soo
    • Korean Journal of Food Science and Technology
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    • v.9 no.2
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    • pp.116-122
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    • 1977
  • The volatile flavor components of Kimchis were identified and the volatiles of fermented Kimchis (1.29% NaCl and 4.89 NaCl) were compared with those of raw Kimchi (1.29% NaCl). After the existence of carbonyls and sulfur compounds were confirmed by precipitation method, vacuum distillation was carried out to collect the volatiles of Kimchis in traps submerged in ice+salt, dryice-acetone and liquid N, respectively. The volatile flavor components were identified by GLC. The results were; 1. 17 volatile flavor components of Kimchis were identified by comparison of retention time with those of known compounds and acetaldehyde, acetone, ethanol, ethyl sulfide were positively identified by m.p., IR, UV, TLC. etc. 2. Ethanol was the most abundant volatiles of Kimchis and the content was much higher in fermented low salt Kimchi than in unfermented low salt Kimchi. 3. On the contrary, acetaldehyde and volatile sulfur compounds were reduced in fermented Kimchis, especially in fermented low salt Kimchi.

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Nonlinear Dielectric Properties of Amorphous copolymers (무정형 고분자 재료의 비선형 유전특성)

  • Roh, Il-Soo;Hwang, Jung-Youn;Kang, Dae-Ha;Lee, Duck-Chool
    • Proceedings of the KIEE Conference
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    • 1999.07d
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    • pp.1563-1565
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    • 1999
  • Linear and nonliear complex permittivities have been measured for amorphous copolymers of vinylidene cyanide (VDCN) with vinyl acetate (VAc), vinyl propionate (VPr), vinyl benzoate (VBz), styrene (St) and methyl methacrylate (MMA). It is found that the third order permittivity ${\varepsilon}_3$ depends upon frequency according to a function ${\Delta}_{{\varepsilon}_3}/(1+i{\omega}{\tau}_^3)$ while the linear permittivity obeys a Debye function ${\Delta}_{{\varepsilon}_1}/(1+i{\omega}{\tau}_1)$. Experimental results are well fitted by the above predicted functions except at low frequencies where dc conduction dominates. The ${\tau}_1$ and ${\tau}_3$ are nearly equal, and depend upon temperature according to a WLF form. The relaxation strength ${\Delta}_{{\varepsilon}_1}$ depends upon comonomers ranging from $130_{{\varepsilon}_0}$(VAc) to $20{{\varepsilon}_0}$(MMA). The ${\Delta}_{{\varepsilon}_3}$ is negative and depends more strongly upon comonomers. Combined knowledge about linear and nonlinear permittivities predicts very large correlation factors which indicates strongly cooperative dipolar motions in those amorphous copolymers.

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PHENOLOXIDASE AND ANTIOXIDANT IN KOREAN GINSENG (고려인삼에 있어서의 페놀 산화효소의 항산화물질)

  • Park E.Y.;Luh B.S.;Branen A.L.
    • Proceedings of the Ginseng society Conference
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    • 1984.09a
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    • pp.257-275
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    • 1984
  • Enzymatic browning is considered desirable in tea and tobacco processing but undesirable in many fruits processing at the present time. It is necessary to understand the nature of the enzyme, phenoloxidase, in order to control browning reactions, and extend its effects to formation of browning products as antioxidants in ginseng. Ginseng exhibits antioxidant activity when incorporated with turkey dark meat patties. The activity in red ginseng showed about two times stronger than white ginseng. One of the phenolic antioxidants from fresh, white and reprocessed white ginseng was identified as phenol 2.6 Bis(1.1 dimethyl ethyl) 4-methyl among several unknown compounds by GC/mass spectrometer. In red ginseng, no phenol 2.6 Bis (1.1 dimethyl ethyl) 4-methyl was detected, the compound may be polymerized by phenoloxidase and form some higher molecular compounds which may possess high antioxidant activity. Phenoloxidase isozymes in fresh Korean ginseng (panax ginseng C.A. Meyer) were extracted with phosphate buffer at pH 7.3. The isozymes were purified through ammonium sulfate fractionation, dialysis and chromatography on a DEAE-cellulose column. Two groups of phenoloxidase were shown to be present, one in the floating agglomerated group and the other in the precipitate. group from the 0.85 saturation ammonium sulfate. The DEAE-cellulose column chromatography, the phenoloxidase isozyme present in the precipitate appears as the first peak (I), and that in the agglomerate in the second peak (II). Isozyme I showed higher activity with catechin and catechal, and isozyme II showed higher activity with p-cresol. The isozyme showed two optimum pH activity one at pH 4.5 and the other at 8.5 with catechin as substrate. Korean ginseng phenoloxidase has high heat stability. When heated at $75^{\circ}C$ for 2 hours, its activity remained $90\%\;and\;80\%$ on phenoloxidase I and II respectively. Phenoloxidase I was most active on (+) catechin followed by p-cresal, catechol and epicatechin. Phenoloxidase II was most active on p-cresal followed by (+) catechin, catechol, p-coumanic acid and epicatechin. Sodium bisulfite, sodium cyanide, ascorbic acid glutachion in the oxidized form, sodium diethyl dithiocarbomate and ethylendiamine tetra acetate (EDTA) acted as inhibitors. Red ginseng color development was initiated by phenoloxidase and finished by a followed sun drying process. The antiaging activity of ginseng may be initiated by the antioxidant in the ginseng.

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Protective Effects of Ginsenosides on Cyanide-induced Neurotoxicity in Cultured Rat Cerebellar Granule Cells

  • Seong, yeon-Hee;Koh, Sang-Bum;Jo, Soon-Ok
    • Journal of Ginseng Research
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    • v.24 no.4
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    • pp.196-201
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    • 2000
  • Effects of ginsenosides on NaCN-induced neuronal cell death were studied in cultured rat cerebellar granule cells. NaCN produced a concentration-dependent (1-10 mM) reduction of cell viability (measured by frypan blue exclusion test), that was blocked by N-methyl-D-aspartate receptor antagonist (MK-801) and L-type Ca$\^$2+/ channel blocker (verapamil). Pretreatment with ginsenosides (Rb$_1$, Rc, Re, Rf and Rg$_1$) significantly decreased the neuronal cell death in a concentration range of 0.5∼5$\mu\textrm{g}$/ml. Ginsenosides Rb$_1$ and Rc (5 $\mu\textrm{g}$/ml) inhibited glutamate release into medium induced by NaCN (5 mM). NaCN (1 mM)-induced increase of [Ca$\^$2+/], was significantly inhibited by the pretreatment of Rb$_1$ and Rc (5 $\mu\textrm{g}$/ml). Other ginsenosides caused relatively little inhibition on the elevation of glutamate release and of (Ca$\^$2+/). These results suggest that the NaCN-induced neurotoxicity was related to a series of cell responses consisting of glutamate release and [Ca$\^$2+/]i elevation via glutamate (NMDA and kainate) receptors and resultant cell death, and that ginsenosides, especially Rb$_1$ and Rc, prevented the neuronal cell death by the blockade of the NaCN-induced Ca$\^$2+/influx.

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