• Bulletin of the Korean Chemical Society
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• 제16권7호
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• pp.634-641
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• 1995

The metal-carbon σ-bond cluster complexes 1-Mn(CO)5-2-R-1,2-C2B10H10 (R=CH3 Ia, C6H5 Ib) have been prepared in good yields from readily available carboranyl lithium complexes, 1-Li+-2-R-1,2-C2B10H10- (R=CH3, C6H5), by direct reaction with (CO)5MnBr. These manganese metal complexes are rapidly converted to the corresponding manganese metal carbene complexes, 1-[(CO)4Mn=C(OCH3)(CH3)]-2-R-1,2-C2B10H10 (R=CH3 IIIa, C6H5 IIIb), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3. The crystal structure of IIIb was determined by X-ray diffraction. Thus, complex IIIb crystallizes in the orthorhombic space group P212121 with cell parameters a=15.5537(5), b=19.0697(5), c=7.4286(3) Å, V=2203.4(1) Å3, and Z=4. Of the reflections measured a total of 3805 unique reflections with F2>3σ(F2) was used during subsequent structure refinement. Refinement converged to R1=0.053 and R2=0.091. Structural studies showed that the manganese atom had a slightly distorted pseudo-octahedral configuration about the metal center with the carbene and ortho-carborane occupying the equatorial plane cis-orientation to each other.

• Bulletin of the Korean Chemical Society
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• 제18권10호
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• pp.1050-1052
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• 1997

The complexes M(CO)4-1,2-(PPh2)2-1,2-C2B10H10 (M=Cr 2a, Mo 2b, W 2c) have been prepared in good yields from readily available bis-diphenylphosphino-o-carboranyl ligand, closo-1,2-(PPh2)2-1,2-C2B10H10 (1), by direct reaction with Group Ⅵ metal carbonyls. The infrared spectra of the complexes indicate that there is an octahedral disposition of chelate bis-diphenylphosphino-o-carboranyl ligand around the metal atom. The crystal structure of 2a was determined by X-ray diffraction. Complex 2a crystallizes in the monoclinic space group P21/n with cell parameters a = 12.2360(7), b = 17.156(1), c = 16.2040(6) Å, V = 3354.1(3) Å3, and Z =4. Of the reflections measured a total of 2514 unique reflections with F2 > 3σ(F2) was used during subsequent structure refinement. Refinement converged to R1 = 0.066 and R2 = 0.071. Structural studies showed that the chromium atom had a slightly distorted pseudo-octahedral configuration about the metal center with two phosphine groups of o-carborane occupying the equatorial plane cis-orientation to each other. These metal carbonyl complexes are rapidly converted to the corresponding metal carbene complexes, [(CO)3M=C(OCH3)(CH3)]-1,2-(PPh2)2-1,2-C2B10H10 (M= Cr 3a, Mo 3b, W 3c), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3.

• 한국응용과학기술학회지
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• 제17권2호
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• pp.113-119
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• 2000

Alkylation of phenol with tert-butanol in the liquid phase on mordenite was studied. The influence of many reaction parameters such as calcination temperature, reaction temperature, t-butanol/phenol molar ratio on catalytic properties was discussed. The main products were 2,4-di-t-butylphenol, o-t-butylphenol, p-t-butylphenol, the last of these was wanted product. In order to enhance the selectivity of p-t-butylphenol, optimum conditions were recommended at $500^{\circ}C$ calcination temperature, $140^{\circ}C$ reaction temperature, 1.0 molar ratio of reactants over mordenite. P-t-butylphenol was formed with 90% isomer selectivity at optimum conditions after 4hr reaction. On the basis of the behavior obtained in the cases mentioned, optimum conditions and catalytic properties for t-butylation of phenol were provided.

• Bulletin of the Korean Chemical Society
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• 제26권6호
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• pp.871-877
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• 2005

Recent progress in the filed of transition-metal mediated C-H bond activation has had a great influence on organic synthesis. Among such transition-metal catalyzed reactions, ortho-functionalization via the chelationassisted strategy has been paid great attentions as one of the powerful methodologies for converting aromatic compounds into ones that are more functionalized at the exclusively ortho-position. In this context, various transition metal-catalyzed ortho-functionalizations such as alkylation, alkenylation, silylation and carbonylation are described briefly and their prospects are suggested.

• Bulletin of the Korean Chemical Society
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• 제12권4호
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• pp.392-397
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• 1991

A stereocontrolled synthesis of (${\pm}$)-isocomene (1) via selective monoketalization of tricyclo[6.3.0.$0^{1.5}$]undeca-4,7-dione(13) was reported. Grignard reaction of bicyclic enone 10, which was prepared from 2-methyl-1,3-cyclopentadione, gave the 1,4-addition product 11. The subsequent aldol condensation product 12 was converted to mesyl derivative 13. Transformation from 13 to the desired product 19 was achieved by a series of reactions, i.e., the selective monoketalization at C-4 carbonyl group, the elimination of a mesyl group, Birch alkylation, methylation at C-6, the reduction of carbonyl group, the dehydration of alcohol 18, and hydrolysis of the ketal group.

• 대한방사성의약품학회지
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• 제2권1호
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• pp.9-16
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• 2016

Carbon-11 is one of the most sensitive and desirable positron emission tomography radio-isotope, which offers the capacity to be incorporated, through a covalent bond, into biologically active molecules without altering their biological properties. Carbon-11 can be obtained from the cyclotron with two different chemical forms: $[^{11}C]CO_2$ and $[^{11}C]CH_4$. [$^{11}C$]Methyl iodide has been widely used as a highly reactive labelling precursor that can be applied to label carbon-11 with biologically active molecules via alkylation of N-, O-, or S-nucleophiles. A more recent and still challenging labeling method is transition metal mediated $^{11}C$-carbonylation. Advances in organic chemistry, radiochemistry and improved automated techniques greatly encourage researchers to develop more carbon-11 labelled radiotracers for molecular imaging studies. This mini-review will introduce a historical track of carbon-11 chemistry combining with examples and its role in near future.

• Tribology and Lubricants
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• 제32권5호
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• pp.141-146
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• 2016

The diketopyrrolopyrrole (DPP) pigment is a bicyclic 8-π-electron system containing two lactam units. Typical DPP derivative pigments have melting points of over 350°C and very low solubility in most solvents, and show absorption in the visible region with a molar extinction coefficient of 33,000 dm²mol⁻¹ and strong photoluminescence with maxima in the range 500–600 nm. X-ray structure analyses of DPP show that the whole molecule is almost in one plane. The phenyl rings are twisted out of the heterocyclic plane and the intermolecular hydrogen bonding between neighboring lactam NH and carbonyl units influences the structure of the DPP pigment in the solid state. In this study, mono-N-alkylation and mono-N-arylation were undertaken for Pigment Red 264 or Pigment Orange 73 with alkyl halide and aryl halide, respectively, in the presence of sodium tert-butoxide as a base catalyst to improve the solubility of DPP pigments and their application as CO₂ indicators. The synthetic yield was in the range 11–88%. The indicator dyes are highly soluble in organic solvents and shows pH-dependent absorption (λ_max 501 and 572 nm for the protonated and deprotonated forms, respectively) and emission (λ_max 524 and 605 nm for the protonated and deprotonated forms, respectively) spectra. The mono-N-alkylated and mono-N-arylated DPP pigment was identified by ¹H-NMR (¹H-Nuclear Magnetic Resonance Spectrometer), FT-IR (Fourier Transform Infrared Spectroscopy), and MS (Mass Spectrometry). According to the results of color and hue properties obtained by a color matching analyzer, the synthesized DPP pigment material can be used as a CO₂ indicator.

• Archives of Pharmacal Research
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• 제19권1호
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• pp.62-65
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• 1996

A homologous series of twenty, hitherto unreported, analogues of 5-halosubstituted $1, 3-Bis(\omega-cyanoalkyl)uracil$acyclic nucleosides were synthesized by the series of alkylation reactions of 5-halouracils with the corresponding chloroacetonitrile, chloropropionitrile, chlorobutyronitrile and 5-chlorovaleronitrile $(Cl-(C_ 2)_n-CN: n=l, 2, 3, 4)\; in\; anhydrous\; DMSO\; (or DMF)/K_2CO_3(or NaH)\; under\; 75^{\circ}C$ temperature. Antitumor activities for the synthesized compounds were determined against three cell lines (FM-3A cell, P-388 cell and U-938 cell lines). The compounds that exhibited moderate activity to significant activity, included la-b, 2a-b, 3a-c, and 4a, whose compounds were active against P-388, FM-3A and U-937 cell lines with the compounds la, lb, and 2a, showing significant antitumor activity (inhibitory concentrations $(IC_{50})$ ranged from 2.2 to $7.0\mug/ml$). Their strucrure-activity relationship did not show any activity differences in their effective chain length (methyl, ethyl, propyl, butyl) in 1, 3-bis(.omega.-cyanoalkyl) uracils.

• Bulletin of the Korean Chemical Society
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• 제25권11호
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• pp.1635-1640
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• 2004

The cyclophanes 1a-d containing two benzo[b]furan rings connected by various bridges have been prepared and their binding behaviors with N-benzylphenethylammonium cation 2 were examined by NMR titration method. The successive alkylation reactions of 4-hydroxyl groups and then 2-hydroxyl groups of 2,4-dihydroxybenzophenonse gave macrocycles 5a-c. Photoirradiation of the macrocycles 5a-c with 350 nm mercury lamp followed by dehydration afforded the cyclophanes 1a-c. Hydrolysis of two ester groups pendant on a bridge of 1b produced the carboxyl group-containing cyclophane 1d. The cyclophane 1a having a p-xylene bridge showed 1 : 1 binding with 2 with the binding constant of $36{\pm}6M^{-1}$ in 3 : 1 $CDCl_3$/methanol-$d_4$ solvent, while 1b and 1c which have neutral flexible bridges exhibited no appreciable binding with 2. The disodium salt of 1d showed much higher binding affinity for 2 forming 1 : 1 and 1 : 2 complexes.

• 대한화학회지
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• 제36권4호
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• pp.598-602
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• 1992

2-Piperidylglycine은 항종양제 593A의 합성을 위한 모델이 될 수 있다. 2-Piperidylglycine은 piperidine의 C-2 위치에 glycine 동등체를 도입하여 합성할 수 있다. ${\delta}$-Valerolactam에 trimethyl oxonium tetrafluoroborate를 가하여 2-methoxy-1-piperideine을 합성하였다. 이 imino ether는 glycine 동등체인 ethyl phthalimidoacetate와 반응하지 않았으나 ethyl nitroacetate와는 축합하여 ethyl nitro-2-piperidylene acetate를 주었다. 이를 Pt/C 촉매하의 수소첨가로 ethyl 2-piperidyl glycinate을 얻을 수 있었는데 축합물인 ethyl nitro-2-piperidylene의 이중결합이 Z-configuration을 가져 ethyl 2-piperidyl glycinate는 항종양제 593A와 다른 입체화학을 가지게 된다.