• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.49-53
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• 2013

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

• Natural Product Sciences
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• v.25 no.1
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• pp.49-58
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• 2019

Eleven steroid hormones (SHs: androstene-3,17-dione, estrone, ${\beta}$-estradiol, ${\alpha}$-estradiol, testosterone, dehydroepiandrosterone, $17{\acute{a}}$-hydroxyprogesterone, medroxyprogesterone, megestrol acetate, progesterone, and androsterone) were detected from New Zealand deer (Cervus elaphus var. scoticus) velvet antler (NZA, 鹿茸 ). A method for the quantification of eleven SHs was established by using ultraperformance liquid chromatography (UPLC)-MS/MS. The linearities ($R^2$ > 0.991), limits of quantification (LOQ values, 0.3 ng/mL to 23.1 ng/mL), intraday and interday precisions (relative standard deviation: RSD < 2.43%), and recovery rates (97.3% to 104.6%) for all eleven SHs were determined. In addition, a method for the quantification of three 7-oxycholesterols (7-O-CSs: 7-ketocholesterol, $7{\alpha}$-hydroxycholesterol, and $7{\beta}$-hydroxycholesterol) in the NZA was established by using an HPLC-photodiode array (PDA) method. The linearities ($R^2$ > 0.999), LOQ values (30 ng/mL to 350 ng/mL), intraday and interday precisions (RSD < 1.93%), and recovery rates (97.2% to 103.5%) for the three 7-O-CSs were determined. These quantitative methods are accurate, precise, and reproducible. As a result, it is suggested that the five steroid compounds of androstene-3,17-dione, androsterone, 7-ketocholesterol, $7{\alpha}$-hydroxycholesterol, and $7{\beta}$-hydroxycholesterol could be marker steroids of NZA. These methods can be applied to quantify or standardize the marker steroids present in NZA.

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1059-1063
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• 1998

Regiospecific total syntheses of (±)-11-deoxy-4-methoxy-10-oxo-βrhodomycinone (21a) and (±)-11-deoxy-1-methoxy-10-oxo-β-rbodomycinone (21b) are described. 2-(2-Bromoethyl)-1,3-dioxane (6) was transformed to naphthalenone 12, which was condensed with (phenylsulfonyl)-isobenzofuranone 13 to afford 7,8-dihydro-9-ethyl-6-hydroxy-4-methoxynaphthacen-5,12-dione (15). Epoxide 16 prepared from olefinic compound 15, reacted with HF/Pyr (7:3) to give 17. Dihydroxylation of 17 with t-BuOK/P(OMe)3/O2, selective cis-diol protection of mixed compounds 18 with phenylboronic acid in toluene, separation of cis-boronate 19 and trans-diol 20 by column chromatography on silica gel, and cleavage of the boronate group of 19 with 2-methylpentane-2,4-diol in acetic acid completed the construction of 21.

• YAKHAK HOEJI
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• v.31 no.1
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• pp.40-41
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• 1987

4-Hydroxy-2H-1, 2-benzothiazine-3-carboxylic acid 1a was reacted with 2 equivalents of dicyclohexylcarbodiimide (DCC) to give 2-cyclohexyl-3-cyclohexylimino-4,5-dihydro-1H-imidazo [1,5-b][1,2] benzothiazine-10, 10a-dyhydro-1,10-dione 5,5-dioxide 2a and dicyclohexylurea (DCU). On the other hand 2-substituted-4-hydroxy-2H-1, 2-benzothiazine-3-carboxylic acid 1,1-dioxide 1b or c was reacted with DCC to give 2-cyclohexylimino-3-cyclohexyl-5-alkyl-4-oxo-2,5H-1,3-oxazino [5,6-c]-1,2-benzothiazine 6,6-dioxide 2b or c and DCU.

• Bulletin of the Korean Chemical Society
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• v.21 no.8
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• pp.797-800
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• 2000

The reaction of o-acylthiophenacyl chloride 5a with onc equivalent ofsodium azide in aqueous acetone at-10~ $-5^{\circ}C$ gave 2,9-dimethyl-6H,I3H-dibenzo[d,i][1,6]dithiecin-7,14-dione 7(10%),acyclic dimer 8(64%),and tri-mer 9 (8%). Dimer 8 and trimer 9 we re converted readily to 7 under the similar conditions at room temperature in yields of 72% and 53%,respectivel. Also, one pot synthesis of 7 (64%, 45%) from the reaction of 5a or 5b with two equivalents of sodium azide at room temperature was very successful.

• Bulletin of the Korean Chemical Society
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• v.24 no.12
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• pp.1767-1770
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• 2003

A simple, rapid and sensitive spectrophotometric method is herewith proposed for the determination of copper(II) by using diamine-dioxime ligand, meso-3,6,6,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime or meso-HexaMethyl Propylene Amine Oxime (meso-HMPAO). This method is based on the formation of a stable 1 : 1 red-pink complex between copper(II) and meso-HMPAO in aqueous solution. Absorption measurements were carried at 497 nm, with a molar absorptivity value of 338 L $mol^{-1}\;cm^{-1}$. Beer's law was obeyed over the concentration range of 0.5-370 ${\mu}$g $mL^{-1}$ with a Sandell's sensitivity value of 0.18 ${\mu}$g $cm^{-2}$. The proposed method has been successfully applied for determination of copper(II) in foodstuffs and pharmaceutical samples. The results obtained from this method are comparable with those obtained AAS.

• Bulletin of the Korean Chemical Society
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• v.12 no.4
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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.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2494-2498
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• 2012

Preparation of several new spirocyclic mercapto derivatives is described. Thiol protection on multi-carbonyl compounds allows of high sulfur content necessary to induce high refractive index. Condensation of 1,3-dimercapto-2-propanol and cyclohexanone followed by successive oxidation and thioacetalization affords a dispirocycle with four sulfurs. Selective S,S-protection of cyclohexane-1,4-dione is achieved with 1,3-dimercapto-2-propanol and 2,3-dimercapto-1-propanol to provide dispirocycles with four sulfurs. Olefine-oxidation of norbornene gives a useful dialdehyde intermediate which is transformed to 1,3-dithiolane for a linearly-bound-cyclic molecule. Refractive index of linearly-bound-cycles was below 1.60 and dispirocycles exhibited high refractive index of 1.57-1.69.

• Bulletin of the Korean Chemical Society
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• v.24 no.8
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• pp.1091-1096
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• 2003

The effects of different polarization conditions on vibrational echo signals are systematically explored for the rigid cyclic dipeptide 2,5-diazabicyclo[2,2,2]octane-3,6-dione. An anharmonic vibrational Hamiltonian is constructed by computing energy derivatives to fourth order using density functional theory. Molecular frame transition dipole orientations are then used to calculate polarization dependent orientational factors corresponding to various Liouville space pathways. Enhancement and elimination of specific peaks in twodimensional correlation plots is accomplished by identifying appropriate pulse configurations.

• Journal of Technologic Dentistry
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• v.35 no.3
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• pp.209-218
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• 2013

Purpose: The purpose of this study was to know the availability of two photosensitizers, PD, DA, as a photosensitizer instead of CQ in UDMA dental composite resin. We want to know photopolymerization effect of UDMA unfilled resin and surface hardness of composite resin containing PD and DA were compared with those of CQ, most widely used photosensitizer for dental composite resins. Methods: The photopolymerization effect of UDMA studied by FT-IR spectroscopy increased with irradiation time and the amount of photosensitizer. Knoop hardness of experimental composite resins prepared by the addition of the photosensitizer content and irradiation time. Results: The relative photopolymerization effect of UDMA increased in the order of PD > CQ > DA. The composite resin of UDMA containing DA or PD, which shows better Knoop hardness than that containing CQ. Conclusion: PD and DA show as effective photosensizers, suitable for UDMA dental composite resin compare with a higher efficiency than CQ.