• Title/Summary/Keyword: trans-1,2-Diaminocyclohexane

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Synthesis and Crystal Structure of Nickel(II) Complex of trans-1,2-Diaminocyclohexane (Nickel(II) trans-1,2-Diaminocyclohexane 착물의 합성 및 결정 구조)

  • ;;;;dward R. T. Tiekink
    • Korean Journal of Crystallography
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    • v.12 no.2
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    • pp.88-91
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    • 2001
  • The complex [NiL₃]Cl₂·3H₂O (1) (L=trans-1,2-diaminocyclohexane) has been synthesized and characterized by X-ray crystallography. The compound 1 crystallizes in the cubic space group P2₁3, with a=13.830(1) Å, V=2645.9(2) ų, Z=4, R₁(wR₂) for 1500 observed reflections of [I> 2σ(I)] was 0.0766 (0.2068).

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Cobalt(Ⅲ) Complexes of N,N'-Bis(2(S)-aminopropyl)-1(R),2(R)-trans-1,2-diaminocyclohexane

  • 이동일;전무진
    • Bulletin of the Korean Chemical Society
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    • v.17 no.9
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    • pp.786-790
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    • 1996
  • A novel optically active tetraamine ligand possessing four asymmetric centers, N,N'-bis(2(S)-aminopropyl)-1(R),2(R)-trans-1,2-diaminocyclohexane (SRRS-apchxn) and its cobalt(Ⅲ) complexes, [Co(SRRS-apchxn)X2]n+ (X=Cl-, H2O, X2=CO32-) have been synthesized. This ligand has coordinated stereospecifically to the cobalt(Ⅲ) ion to give only the Λ-uns-cis-(SS) isomer. A trans dichloro complex has been obtained via the stereospecific isomerization of Λ-uns-cis-(SS)-[Co(SRRS-apchxn)Cl2]+ to trans-(SS)-[Co(SRRS-apchxn) Cl2]+ in CH3OH-HCl medium. Ligand and complexes have been characterized by electronic absorption, 1H NMR, CD spectra, and also by elemental analysis. It is of interest that this is one of the few CoⅢ(N4)X2 type complex preparations, which produces such an uns-cis isomer with stereospecificity.

Stereospecific Coordination of 2,2$^\prime$-Diaminobiphenyl in the Square Planar Platinum(Ⅱ) Comdlexes

  • Jun, Moo-Jin;Choi, Sung-Rack
    • Bulletin of the Korean Chemical Society
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    • v.5 no.6
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    • pp.237-240
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    • 1984
  • 2,2'-Diaminobiphenyl platinum (II) complexes of optically active trans-1,2-diaminocyclohexane and 1,2-diaminopropane, [Pt(S,S-chxn)(dabp)]Cl2, [Pt(R,R-chxn)(dabp)]$C_{12}$, [Pt(S-pn)(dabp)]$C_{l2}$, and [Pt(R-pn)(dabp)]Cl2, where S,S-chxn and R,R-chxn are, respectively, S and R isomers of trans-1,2-diaminocyclohexane, and S-pn and R-pn are, respectively, S and R isomers of 1,2-diaminopropane, and dabp the 2,2'-diaminobipheny, have been prepared. The dabp ligand has been found to take the $=delta$ conformation in the S,S-chxn and S-pn platinum (II) complexes, while it takes the $\lambda$ conformation in the R,R-chxn and R-pn platinum (II) complexes.

Development of Ferrocene-Containing Metal Catalysts for Asymmetric Synthesis (페로센을 이용한 비대칭 유기합성용 금속 촉매의 개발)

  • Oh, Yunghee;Choi, Mi-Jin
    • Applied Chemistry for Engineering
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    • v.10 no.5
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    • pp.804-807
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    • 1999
  • New copper complexes with a ligand, L(L=N,N'-cyclohexane bis(ferrocenylmethylene)amine) which was obtained from ferrocene carboxaldehyde and 1,2-diaminocyclohexane with a mole ratio of 2:1, were prepared and characterized. Those were adapted to asymmetric catalysis. The copper(II) complexes do not work in cyclopropanation of styrene and ethyl diazoacetate but copper(I) complex catalyzes. The Cu(I)LOTf (OTf=trifluorometanesulfonate) shows a good regioselectivity giving high trans to cis ratio of up to 80:20.

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Synthesis and Crystal Structure of the Cadmium(II) Complex with Thiocyanate and 1,2-Diaminocyclohexane Ligands (Thiocyanat 및 1,2-Diaminocyclohexane 리간드로 구성된 카드뮴(II) 착물의 합성 및 결정구조)

  • 김인회;서승욱;김종혁;김진규;서일환
    • Korean Journal of Crystallography
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    • v.12 no.4
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    • pp.207-211
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    • 2001
  • The crystal structure of the title complex, Cd(SCN)₂{CH/sub 6/H/sub 10/(NH₂)₂}₂(1) has been analyzed by X-ray single crystallography. The complex 1 crystallizes in the monoclinic system P2₁/ space group with a=11.842(2), b=7.926(2), c=11.291(2) Å, β=106.73(3)°V=1014.8(4)Ų, Z=2, R₁=0.0518 and ωR₂=0.1315 for 1775 independent reflections. The central Cd(II) atom of this com-plex has a slightly distorted octahedral coordination geometry, with the 1,2-Diaminocyclohexane ligands functioning as an N,N'-bidentate and the thiocyanate ligands bonding through the sulfur atom in a trans arrangement.

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Circular Dichroism Spectra on the Counter Ions and the Solvent Dependence of trans-$[Co(R,R-chxn)_2Cl_2]^+$ Complex (trans-[Co(R,R-chxn)$_2Cl_2]^+$ 착물의 대이온 및 용매의존성 원편광이색성 스펙트라)

  • Chang Eon Oh;Yang Kim;Sung Yeul Park;Myung Ki Doh
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.493-499
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    • 1991
  • The circular dichroism (CD) spectrum of trans-[Co(R,R-chxn)$_2Cl_2]^+$ complex with different counter-ions have been measured in several organic solvents, where R,R-chxn is (1R,2R)-1,2-diaminocyclohexane. The observed variations in the CD spectrum of the complex exhibited remarkable solvent dependences. And it has been observed that the degree of the change of CD spectrum in the first absorption band region $(^1A_{2g})$ depends on the donor number (DN) of the solvents. From $^1H$ NMR spectrum, it is interpreted that these variations in the CD spectrum of trans-[Co(R,R-chxn)$_2Cl_2]^+$ complex are due to the favorable interaction between solvent molecules and the equatorial N-H protons of R,R-chxn ligands.

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Chiral Mesoporous Silica for Asymmetric Metal-free Catalysis: Enhancement of Chirality thorough Confinement Space by Plug Effect

  • Jeong, Eun-Yeong;Im, Cheong-Rae;Park, Sang-Eon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.199-199
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    • 2011
  • The addition of a carbanion to ${\yen}{\acute{a}}{\yen}{\hat{a}}$-unsaturated carbonyl compounds is of importance in the C-C bond formation reactions for modern pharmaceuticals and organic synthesis. Recently, heterogeneous asymmetric catalysis became more attractive area of research because of the easy recovery and separation of the catalyst from the reaction system. Most of synthetic methods for heterogeneous catalysts were grafting or immobilization of homogeneous catalyst onto the solid supports. Trans-1,2-Diaminocyclohexane(DACH) and L-proline ligands have been enormously used as chiral ligands in several catalytic transformation under homogenous conditions. Our group prepared l-proline functionalized mesoporous silica was synthesized under acidic condition using a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer template (EO20PO70EO20, Pluronic P-123, BASF). Furthermore, we successfully directly synthesized trans-1,2 diaminocyclohexane functionalized mesoporous silica by using microwave method. The direct functionalization of chiral ligand into the framework of mesoporous materials is expected to be useful for the heterogeneous asymmetric catalysis. So, we adopt the direct synthesis of chiral ligand functionalized mesoporous silica by using thermal and microwave irradiation. Then, chiral ligand functionalized mesoporous silicas were applied to enantioselective asymmetric catalytic reactions.

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A New Class of Platinum (II) Complexes [Pt (trans-1-daeh) (DPPP)] $2NO_3$ and [Pt (trans-1-daeh)(DPPE)] $2NO_3$ Exhibiting Antitumor Activity and Nephrotoxieity (새로운 Platinum (II) Complex ([Pt (II)(trans-1-dach)(DPPP)] $(NO_3)_2$와 [Pt (II)(trans-1-dach)(DPPE)] $(NO_3)_2$의 항암효과 및 신독성에 관한연구)

  • Jung, Jee-Chang;Yoon, Chin-Hee;Chang, Sung-Goo;Lee, Kyung-Tae;Rho, Young-Soo
    • The Korean Journal of Pharmacology
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    • v.29 no.2
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    • pp.283-295
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    • 1993
  • Pt-complexes is currently one of the most compounds used in the treatment of solid tumors. However, its used is limited by severe side effects such as renal toxicity. Our platinum-based drug discovery program is aimed at developing drugs capable of diminishing toxicity and improving antitumor activity. We synthesized new Pt (II) complex analogues containing 1, 2-diaminocyclohexane (dach) as carrier ligand and 1, 3-bis (diphenylphosphino) propane (DPPP)/1,2-bis (diphenylphosphino) ethane (DPPE) as a leaving group. Furthermore, nitrate was added to improve the solubility. A new series of (KHPC-001) [Pt (trans-1-dach)(DPPP)] $2NO_3$ and (KHPC-002) [Pt (trans-1-dach)(DPPE)] $2NO_3$ were synthesized and characterized by their elemental analysis and by various spectroscopic techniques [infrared (IR), $^{13}carbon$ nuclear magnetic resonance (NMR)]. KHPC-001 and KHPC-002 demonstrated acceptable antitumor activity aganist P-388, L-1210 lymphocytic leukemia cells and significant activity as compared with that of cisplatin. The toxicity of KHPC-001 and KHPC-002 was found quite less than that of cisplatin using MTT, $[^3H]$ thymidine uptake and glucose consumption tests in rabbit proximal tubule cells and human kidney cortical cells.

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Identification of Major Metabolites of New Platinum(II) Complexes in Rats (새로운 백금 착체(II) 화합물의 흰쥐 혈장에서 대사체 확인)

  • Kim, Jong-Whan;Jo, Yo-Na;Rho, Young-Soo;Seo, Seong-Hoon;Jung, Jee-Chang;Chang, Sung-Goo;Lee, Kyoe-Heung;Lee, Joo-Han;Lee, Kyung-Tae
    • Journal of Pharmaceutical Investigation
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    • v.28 no.3
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    • pp.171-175
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    • 1998
  • KHPC-002 $[(trans-l-diaminocyclohexane-bis-l,2(diphenylphosphinoethane)platinum)\;{\cdot}2NO_3]$ and $KHPC-006[(cis-diaminocyclohexane-bis-1,2(diphenylphosphinoethane)platinum)\;{\cdot}2NO_3]$ were synthesized as candidates for third platinum antitumor agent. Before their pharmacokinetic study, we optimized the analytical condition with HPLC and identified the major metabolites in the rat plasma. HPLC analysis by $C_{18}$ reverse-phase column showed that standard peak of both compounds appeared rapidly at around 1 minutes, whereas metabolites of KHPC-002 and KHPC-006 which were extracted from plasma after single I.V. administration in rats or incubation for 24 hr at $37^{\circ}C$ showed retention time of $10{\sim}11$ minutes. These metabolites were identified as the major compound by Matrix Associated Laser Deposition/Ionization (MALDI), which only lose the 2 molecules of $NO_3$. Based on these results, we suggest that the major metabolites of KHPC-002 and KHPC-006 were [trans-l-diamino-cyclohexane-bis-l,2(diphenylphosphinoethane)platinum] and [cis-diaminocyclohexane-bis-l.2(diphenylphosphinoethane)platinum], respectively.

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