• Archives of Pharmacal Research
• /
• v.17 no.3
• /
• pp.204-206
• /
• 1994

A regioselective perparation of 10-methoxy-11-hydroxyaporphine ("Apocodeine, 1b") form (R, S)-10, 11-dihydroxyaporphine(apomorphine, 1a) is described. The isopropylidene ketal ring of 10, 11-(isopropylidenyldioxy) aporphine (2) obtained by the isopropylidenation of apomorphine, was regioselectively opened by the ten equivalent of timethylaluminum to give 100-hydroxy-11-t-butyloxyaporphine (3). The free 10-hydroxyl position of 3 was methylated with methyl p-toluenesulfonate/NaH, and afforded 10-methoxy-11-t-butyloxyaporphine (4) in high yield. Selective debutylation gave the desired 10-methoxy-11-hydroxyaporphine("apocodeine", 1b) in good yield.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.3
• /
• pp.314-319
• /
• 1998

One flask synthesis of dithienylmethane and difurylmethane is reported. The reaction of aldehydes with excess furan or thiophene affords the meso-phenyldithienylmethane (DTM) and meso-phenyldifurylmethane (DFM), respectively. The reaction is catalyzed with trifluoroacetic acid or with BF3·O(Et)2. An acyl group is selectively introduced in 1 and 9 position of difurylmethane and dithienylmethane by use of an acid chloride and tin (IV) chloride. The reduction of resulting 1,9-bisacyldifurylmethane or 1,9-bisacyldithienylmethane affords the corresponding 1,9-bis-diol. An acid catalyzed condensation of diol with meso-phenyldipyrromethane followed by oxidation with DDQ gives the porphyrins. The reaction resulted meso-5,10,15,20-tetraphenyl-21,22-dithiaporphyrin (SSNN) or 15-mesityl-5,10,20-triphenyl-21,22-dioxaporphyrin (OONN), respectively. The formation of small amount of meso-tetraphenylporphyrin (TPPH2) is also observed. The formation of TPP indicates that meso-phenyldipyrromethane is reversibly cleaved and form pyrrole and pyrrylbenzylcarbocation during the condensation. The proton nmr and electronic spectrum of the SSNN and OONN porphyrins are somewhat different from the previously synthesized meso-5,10,15,20-tetraphenyl-21,23-dithiaporphyrin (SNSN) or meso-5,10,15,20-tetraphenyl-21,23-dioxaporphyrin (ONON).

• YAKHAK HOEJI
• /
• v.48 no.2
• /
• pp.141-146
• /
• 2004

Selective COX-2 inhibitors were expected to retain anti-inflammatory activity by inhibition of prostaglandin production with reduction of gastric and renal side effect associated with non-steroidal anti-inflammatory drugs. This study reported the syntheses of novel 2-thiohydantoin and hydantoin derivatives which have the structure of 5-membered heterocyclic ring substituted with two aryl groups, phenyl group at 5-position and p-sulfamylphenyl or p-methoxyphenyl group at 1-position. These synthetic compounds showed significant COX-2 activities in vitro screening. Among them, 5-phenyl-2-thiohydantoin and hydantoin substituted with benzyl group at 3-position, compounds 5 and 8, could be considered as lead compounds with $IC_{50}$/=13.13∼18.78 $\mu\textrm{g}$/$m\ell$ for the development of COX-2 inhibitors.

• YAKHAK HOEJI
• /
• v.29 no.1
• /
• pp.39-42
• /
• 1985

Betaines of bicyclic imidazo-thiazoles were synthesized by the reaction of clectrophiles such as methyl isocyanate, methyl isothiocyanate, allyl isothiocyanate and ketene with 3-methyl and 3-phenyl-5, 6-dihydroimidazo [2,1-b] thiazole. In this reaction, the methyl group which was substituted at 3-position increased the yields of the products in comparison with those from phenyl group substituted substrates. Also, the betaines reacted with methyl iodide to give imidazo-thiazolium salts which were unstable at high temperature and converted the quaternary ammonium salts of original biheterocycles.

• Journal of Environmental Science International
• /
• v.20 no.6
• /
• pp.687-700
• /
• 2011

A new $N_3-O_2$ pentadentate ligand, H-BHPT, was synthesized. Hydrochloric acid salts of Br-BHPT, Cl-BHPT, $CH_3O$-BHPT and $CH_3$-BHPT, having Br-, Cl-, $CH_{3-}$ and $CH_3O-$ substituents at the para position of the phenol hydroxyl group of H-BHPT were synthesized. Hydrochloric acid salts of 3OH-BHPT and 4OH-BHPT, having different position of the phenol hydroxyl group of H-BHPT were also synthesized. The synthesis of each ligand was confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible, and mass spectra. The calculated proton dissociation constants ($log{K_n}^H$) of the phenol hydroxyl group and secondary amine group of the synthesized $N_3-O_2$ ligands showed five steps of the proton dissociations. The order of the overall proton dissociation constants ($log{\beta}_p$) of the ligands was Br-BHPT < Cl-BHPT < H-BHPT < $CH_3O$-BHPT < $CH_3$-BHPT. The order agreed with that of Hammett substituent constants (${\delta}_p$). However, dissociation steps of 3OH-BHPT were four and that of 4OH-BHPT was three. The calculated stability constants ($logK_{ML}$) between the ligands and transition metal ions agreed with the order of $log{\beta}_p$ values of the ligands. The order of the stability constants between the transition metal ions with the synthesized ligands was Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order agreed well with that of the Iriving-Williams.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2003.07b
• /
• pp.735-738
• /
• 2003

Downsizing electronics requires precision position control with an accuracy of sub-micron order, which demands development of ultra-fine displacive devices. Piezoelectric transducer is one of devices transferring electric field energy into mechanical energy and being capable for fine displacement control. The transducer has been widely used as fine Position control device Multilayer piezoelectric actuator, one of typical piezo-transducer, is fabricated by stacking alternatively ceramic and electrode layers several hundred times followed by cofiring process. Electrode material should be tolerable in the firing process maintaining at ceramic-sintering temperatures up to $1100{\sim}1300^{\circ}C$. Ag-Pd can be used as stable electrode material in heat treatment above $960^{\circ}C$. Besides, adding small quantity ceramic powder allow the actuator to be fabricated in a good shape by diminishing shrinkage difference between ceramic and electrode layers, resulting in avoidance of crack and delamination at and/or nearby interface between ceramic an electrode layers. This study presents synthesis of nano-oxide-added Ag/Pd powders and its feasibility to candidate material tolerable at high temperature. The powders were formed in a co-precipitation process of Ag and Pd in nano-oxide-dispersed solution where Ag and Pd precursors are melted in $HNO_3$ acid.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.9
• /
• pp.2649-2654
• /
• 2014

Synthesis of north-5'-methylbicyclo[3.1.0]hexyl adenine and hypoxanthine nucleosides with an ethenyl group at C3' position was successfully achieved by a highly facile method. Methylbicyclo[3.1.0]hexanone (${\pm}$)-7 with three contiguous chiral centers and its epimer (${\pm}$)-6 was remarkably simply constructed only by four steps involving a carbenoid insertion reaction in the presence of rhodium (II) acetate dimer as a metal catalyst, giving a correct relative stereochemistry of the generated three chiral centers. Due to steric hindrance from the concave face of the bicyclo[3.1.0]hexanone system, a Grignard reaction of (${\pm}$)-7 with ethenylmagnesium bromide showed exclusive diastereoselectivity towards the b-face. The Grignard reaction chemoselectively proceeded without reacting with ester functionality. Coupling reaction of glycosyl donor (${\pm}$)-11 with 6-chloropurine nucleobase afforded only the desired $N^9$-alkylated nucleoside without the formation of $N^7$-regioisomer. By the conventional method, 6-chloro group was converted into 6-amino and 6-hydroxy groups to give the desired adenine and hypoxanthine bicyclo[3.1.0]hexyl carbanucleosides with 3'-ethenyl group, respectively.

• Bulletin of the Korean Chemical Society
• /
• v.24 no.4
• /
• pp.460-466
• /
• 2003

For the drug master file (DMF) of ketoconazole, four impurities (1-4) contained in ketoconazole were synthesized. During the synthesis of 2, a new synthetic method of 1,4-dihydropyrazine was established. To oxidize the aminoalcohol (2j) to the aminal (2j-1), the standard Swern oxidation condition was modified to mask the nucleophilicity of the amino group temporarily using one equivalent of acetic acid. Derivative 3 was synthesized via regioselective bromination at the 2 position of the 4-aminophenol derivative (3a) using $Br_2$ in the presence of p-TsOH. The etherification of aryl bromide with the phenol derivative (1f) was accomplished by a modification of the general Cu-mediated reaction condition using excess 1f itself as a solvent at elevated temperature (190 ℃).

• Journal of Advanced Marine Engineering and Technology
• /
• v.19 no.3
• /
• pp.42-49
• /
• 1995

In this study, the optimum structural modification of the L-type structure by shape changes is suggested. The vibration characteristics of L-type structure are analyzed by the sub-structure synthesis method, and the coordinte sensitivities of each sub-structure are calculated and the change quantities of the positions to be modified are suggested by using the coordinate sensitivities. The results obtained are as follows : 1. The sensitivities of the natural frequency could be calculated by the sensitivity analysis. 2. The change quantities of the position to be modified could be suggested by the optimum structural modification method. 3. The developed program could reduce the process and time of computation, since the sensitivity was directly calculated by differential method, not finite difference method.

• Advances in materials Research
• /
• v.3 no.2
• /
• pp.117-128
• /
• 2014

Processable conducting polyaniline derivative with free amine functional groups was successfully synthesized from the monomer o-phenylenediamine in aqueous hydrochloric acid medium using ammonium persulfate as an oxidative initiator. The synthesized poly(o-phenylenediamine) (PoPD) in critical condition was found to be completely soluble in common organic solvents like dimethyl sulfoxide, N,N-dimethyl formamide etc. From the intrinsic viscosity measurement, the optimum condition for the polymerization was established. The polymer was characterized by ultraviolet visible spectroscopy, Fourier transform infrared spectroscopy, proton magnetic resonance spectroscopy ($^1HNMR$) and thermogravimetric (TGA) analyses. The weight average molecular weights of the synthesized polymers were determined by the dynamic light scattering (DLS) method. From the spectroscopic analysis the structure was found to resemble that of polyaniline derivative with free amine functional groups attached to ortho/meta position in the phenyl ring. However, very little ladder unit was also present with in the polymer chain. The moderate thermal stability of the synthesized polymer could be found from the TGA analysis. The average DC conductivity of $2.8{\times}10^{-4}S/cm$ was observed for the synthesized polymer pellet after doping with hydrochloric acid.