• Title/Summary/Keyword: $^{31}P$ NMR spectroscopy

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Synthesis and Reactivity of the Pentacoordinate Organosilicon and -germanium Compounds Containing the C,P-Chelating ο-Carboranylphosphino Ligand [ο-C2B10H10PPh2-C,P](CabC,P

  • Lee, Tae-Gweon;Kim, Sang-Hoon;Kong, Myong-Seon;Kang, Sang-Ook;Ko, Jae-Jung
    • Bulletin of the Korean Chemical Society
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    • 제23권6호
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    • pp.845-851
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    • 2002
  • The synthesis of the intramolecular donor - stabilized silyl and germyl complexes of the type ($Cab^c.p) MMe_2X$ (2a:M=Si, X=Cl;2b;M= Ge, X=Cl;2e;M=Si,X=H) was achieved by the reaction of $LiCab^c,p$ (1) with $Me_2SiClX$ and $Me_2GeCl_2$ respectively. The intramolecular M←P interacion in 2a-2c is provided by $^1H$, $13^C.$, $31^P$ and $29^Si$ NMR spectroscopy. The salt elimination reactions of dichlorotetramethyldisilane and -digermane with 1 afforded the $bis(\sigma-carboranylphosphino)disilane$ and disgermane [$(Cab^C.P)MMe_2]_2(4a;M$ = Si;4b: M=Ge). The oxidative addition reaction of 4a-4b with $pd_2(dba)_3CHCl_3afforded$ the bis(silyl)-and bis(germyl)-palladium complexes. The chloro-bridged dipalladium complexes were obtained by the reaction of 2a-2b with $pd_2(dba)_3CHCl_3$ The crystal structures of 5a and 7b were determined by X-ray structural studies.

TTF 주게분자의 전구체로서 두 가지 다른 1,3-Dithiole-2-thione 화합물의 합성 및 특성화 (Synthesis and Characterization of Two Different 1,3-Dithiole-2-thiones as the Precursors of TTF Donor Molecule)

  • 김영윤;이하진;남궁성건;홍종기;노동윤
    • 대한화학회지
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    • 제44권6호
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    • pp.513-517
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    • 2000
  • TTF (tetrathiafulvalene) 유도체의 전구체로서 5,6-dimethyl-1,3-dithiolo[4,5-b][1,4]dithiin-2-thione (화합물 3)을 로손반응에 의하여 합성하였다. 치환기의 종류에 따라 1,4-dithiin이나 티오펜이 포함된 두 가지의 서로 다른 생성물이 얻어졌고, 이들은 $^{13}C$ NMR과 고 분해능 전자충돌(HREI) 질량분석 분광학으로 특성화하였다. 화합물 3의 합성은 X-선 구조분석으로도 확인되었다. 결정학적 자료: 삼사정계, 공간군 P1, a=4.145(2)${\AA}$, b=10.600(2)${\AA}$, c=12.279(2)${\AA}$, ${\alpha}=71.440(10)^{\circ},\;{\beta}=84.30(2)^{\circ},\;{\gamma}=87.31(2)^{\circ}$, Z=2, $R(wR_2$)=0.0559(0.1416). 두 가지 생성물의 생성 기구를 비교하여 설명하였다.

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포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화고리 반응 (제 1 보). 불포화카르복실산이 배위된 팔라듐(0, Ⅱ) 착물의 합성과 구조 (Carbonylative Cyclization of Unsaturated Carboxylic Acids by Palladium Complexes with Phosphines(I) Synthesis and Structure of Palladium(O, II) Complexes with Unsaturated Carboxylic Acids)

  • 도명기;정맹준;이동진
    • 대한화학회지
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    • 제37권4호
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    • pp.423-430
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    • 1993
  • $trans-PdEt_2(PMe_3)_2$와 styrene을 반응시켜 얻어진 $Pd(PMe_3)_2$(styrene)에 methacrylic acid와 trans-crotonic acid를 각각 반응시켜 새로운 팔라듐(O)-올레핀착물로서 $(PMe_3)_2Pd{CH_2=C(CH_3)COOH}$(PMe_3)_2Pd{(CH_3)CH=CHCOOH}$를 합성하고, 구조와 특성을 원소분석, IR 및 $^1H-,\;^{13}C-,\;^{31}P-NMR$ 등의 분광학적 방법으로 조사하였다. methacrylic acid 와 trans-crotonic acid에 존재하는 올레핀의 이중결합은 팔라듐(O)에 ${\pi}$-결합을 형성하였고, 카르복실산은 팔라듐에 결합되지 않았음을 알게되었다. 그리고 동일한 반응에서 metallacycle을 형성하는 3-butenoic acid와 비교 검토하였다.

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α-케토안정화된 일리드화 인의 수은(II) 및 은(I) 착물에 대한 X-선 및 분광학적 연구 (X-ray and Spectroscopy Studies of Mercury (II) and Silver (I) Complexes of α-Ketostabilized Phosphorus Ylides)

  • Karami, K.;Buyukgungor, O.;Dalvand, H.
    • 대한화학회지
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    • 제55권1호
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    • pp.38-45
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    • 2011
  • 전이금속 이온인 수은(II) 및 은(I)에 대한 $\alpha$-케토안정화된 일리드화 인 $Ph_3P$=CHC(O) $C_6H_4$-X (X=Br, Ph)의 착물 반응 행동을 연구하였다. 수은(II) 착물 {$HgX_2$ [Y]} 2 ($Y_1$=4-bromo benzoyl methylene triphenyl phosphorane; X=Cl(1), Br(2), I(3), $Y_2$=4-phenyl benzoyl methylene triphenyl phosphorane; X=Cl(4), Br(5), I(6))는 $Y_1$$Y_2$$HgX_2$ (X=Cl, Br, I)와 각각 반응시켜 제조하였다. $\alpha$-케토안정화된 일리드화 인($Y_2$)의 은(I) 착물 [Ag$(Y_2)_2$] X(X=$BF_4$(7), OTf(8))는 이러한 일리드와 AgX(X=$BF_4$, OTf)를 아세톤에서 반응시켜 얻었다. 착물 (1)과 (4)의 결정구조를 고찰하였다. 일리드의 C-배위 이핵착물과 트랜스-구조의 착물$[Y_1HgCl_2]_2$. $CHCl_3$ (1) 및 $[Y_2HgCl_2]_2$ (4)를 형성하는 이들 반응에 대해 단결정 X-선 분석을 통해 고찰하였다. 모든 착물(1-3)은 IR, $^1H$$^{31}P$ NMR 뿐만아니라 $^{13}$CNMR을 통하여 확인하였다.

비스실릴팔라듐(II) 및 백금(II)착물의 합성 및 확인 (Synthesis and Characterization of Bis(silyl) Palladinum and -Platinum(II) Complexes)

  • 최준철;김용주
    • 통합자연과학논문집
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    • 제2권3호
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    • pp.190-193
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    • 2009
  • Bis(silyl)palladinum(II) and -platinum(II) complexes are key intermediates for the synthesis of organic silyllated compounds by the Pd or Pt-catalyzed reactions. Reactions of dialkylpalladinum and -platinum complexes with diphenylsilane gave the bis(silyl)palladinum and -platinum complexe in moderate to good yields. Isolated complexes were characterized by $^1H$, $^{13}C$ and $^{31}P$-NMR spectroscopy and elemental analyses. Some of the complexes were determined by X-ray crystallographic studies.

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Synthesis and Characterization of Dodecanucleotides Containing the XhoI Recognition Sequence with a Phosphorothioate Group at the Cleavege Site

  • 문병조;김상국;김남희;권오신
    • Bulletin of the Korean Chemical Society
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    • 제17권11호
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    • pp.1031-1036
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    • 1996
  • The synthesis and characterization of diastereomeric dodecanucleotides, d[GATCp(S)TCGAGATC], containing recognition sequence of the XhoI restriction endonuclease with a phosphorothioate internucleotidic linkage the cleavage site are described. Rp and Sp form of diastereomerically pure dinucleoside phosphorothioates d[Cp(S)T] were presynthesized and used for the addition to the growing oligonucleotide chain as a block. The stereochemistry of dinucleoside phosphorothioate was assigned by 31P NMR spectroscopy, enzyme digestion, and reverse-phase HPLC. XhoI restriction endonuclease cut only Rp diastereomer d[GATCp(S))TCGAGATC]. The rate of hydrolysis is slower than that of the unmodified dodecamer d[GATCTCGAGATC]. The phosphorothioate nucleotide is using for determination of the stereochemical course of the XhoI catalyzed reaction.

Aminophosphine류가 배위된 전이금속(Pd, Ni) 착물의 촉매반응; I. 탄소-탄소 짝지움 반응 (Catalytic Reactivity of Transition Metal (Pd, Ni) complexes with Aminophosphines; I. Carbon-Carbon coupling reactions)

  • 정맹준;이철재;김동엽
    • 한국산업융합학회 논문집
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    • 제7권1호
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    • pp.107-113
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    • 2004
  • Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

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Syntheses and Reactions of Iridium Complexes Containing Mixed Phosphine-Olefin Ligand: (3-(Diphenylphosphino)propyl)(3-butenyl)phenylphosphine

  • Young-ae W. Park;Devon W. Meek
    • Bulletin of the Korean Chemical Society
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    • 제16권6호
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    • pp.524-528
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    • 1995
  • The reaction of [IrCl(cod)]2 with ppol ligand, Ph2PCH2CH2CH2P(Ph)CH2CH2CH=CH2, in ethanol gives an iridium complex, whose structure is converted from an ionic form, [Ir(cod)(ppol)]Cl·2C2H5OH (1),in polar solvents (ethanol, methanol and acetonitrile), to a molecular form, [IrCl(cod)(ppol)], in non-polar solvents (benzene and toluene). The cationic complexes, [Ir(cod)(ppol)]AsF6·1/2C2H5OH and [Ir(cod)(ppol)]PF6·1/2CH3CN, were prepared to compare with the ionic form by 31P NMR spectroscopy. When carbon monoxide is introduced to 1, cod is replaced by CO to give the 5-coordinated complex, [IrCl(CO)(ppol)]. Hydrogenation of 1-octene was not successful in the presence of 1. In order to verify the reason for 1 not behaving as a good catalyst for hydrogenation, electrophilic reactions with HCl, I2 and HBF4·etherate were performed, which yielded the oxidative addition product, [IrHCl2(ppol)], the substitution product, [IrI(cod)(ppol)], and another cationic product, [Ir(cod)(ppol)]BF4, respectively. Thus, the iridium complex is not sufficiently basic to activate hydrogen atoms or the olefin of the ppol ligand.

Bioactive Levan-Type Exopolysaccharide Produced by Pantoea agglomerans ZMR7: Characterization and Optimization for Enhanced Production

  • Al-Qaysi, Safaa A.S.;Al-Haideri, Halah;Al-Shimmary, Sana M.;Abdulhameed, Jasim M.;Alajrawy, Othman I.;Al-Halbosiy, Mohammad M.;Moussa, Tarek A.A.;Farahat, Mohamed G.
    • Journal of Microbiology and Biotechnology
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    • 제31권5호
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    • pp.696-704
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    • 2021
  • Levan is an industrially important, functional biopolymer with considerable applications in the food and pharmaceutical fields owing to its safety and biocompatibility. Here, levan-type exopolysaccharide produced by Pantoea agglomerans ZMR7 was purified by cold ethanol precipitation and characterized using TLC, FTIR, 1H, and 13C NMR spectroscopy. The maximum production of levan (28.4 g/l) was achieved when sucrose and ammonium chloride were used as carbon and nitrogen sources, respectively, at 35℃ and an initial pH of 8.0. Some biomedical applications of levan like antitumor, antiparasitic, and antioxidant activities were investigated in vitro. The results revealed the ability of levan at different concentrations to decrease the viability of rhabdomyosarcoma and breast cancer cells compared with untreated cancer cells. Levan appeared also to have high antiparasitic activity against the promastigote of Leishmania tropica. Furthermore, levan had strong DPPH radical scavenging (antioxidant) activity. These findings suggest that levan produced by P. agglomerans ZMR7 can serve as a natural biopolymer candidate for the pharmaceutical and medical fields.

Melanogenesis Inhibitory Activity of Epicatechin-3-O-Gallate Isolated from Polygonum amphibium L.

  • Lee, Young Kyung;Hwang, Buyng Su;Hwang, Yong;Lee, Seung Young;Oh, Young Taek;Kim, Chul Hwan;Nam, Hyeon Ju;Jeong, Yong Tae
    • 한국미생물·생명공학회지
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    • 제49권1호
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    • pp.24-31
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    • 2021
  • This study aimed to investigate the melanogenesis inhibitory activity of epicatechin-3-O-gallate (ECG) isolated from Polygonum amphibium L. ECG was isolated from the ethanol extract of P. amphibium L, and its chemical structure was determined using spectroscopic methods such as LC-ESI-MS, 1D-NMR, and UV spectroscopy. ECG inhibited the melanogenesis of B16F10 cells in a dose-dependent manner. Particularly, it decreased the melanin content by 27.4% at 200 µM concentration, compared with the control, in B16F10 cells, without causing cytotoxicity. It is noteworthy that the expression of three key proteins, including tyrosinase, tyrosinase-related protein-1 (TRP-1), TRP-2, and microphthalmia-associated transcription factor (MITF), involved in melanogenesis, is significantly inhibited by ECG. The ECG isolated in this study caused the inhibition of body pigmentation and tyrosinase activity in vivo in the zebrafish model. These results suggest that the ECG isolated from P. amphibium L. is an effective anti-melanogenesis agent.