• Bulletin of the Korean Chemical Society
• /
• v.34 no.1
• /
• pp.174-178
• /
• 2013

A highly reliable dealkylation protocol of alkyl aryl ethers, whose alkyl groups are longer than methyl group, has been developed. We report that various ethyl, n-propyl, and benzyl aryl ethers are successfully cleaved using an ionic liquid, 1-n-butyl-3-methylimidazolium bromide, [bmim][Br], under microwave irradiation. Despite many characteristics such as lower cost and less toxicity of the alkylating agents, and greater hydrophobicity of the products, longer alkyl ethers have been significantly less exploited than methyl ethers, probably due to more difficulty in the deprotection step. Since it has the same advantages as the demethylation method developed by this group including mild conditions, short reaction time, and small use of the ionic liquids, the dealkylation protocol can greatly encourage the broader use of longer alkyl groups in the protection of phenolic groups. As with our previous study of demethylation using [bmim][Br], the microwave irradiation is crucial for the deprotection of longer alkyl aryl ethers. Unlike the conventional heating, which causes either low conversion or decomposition, the microwave irradiation seems to more effectively provide energy to cleave the ether bonds and therefore suppresses the undesired reactions.

• Applied Chemistry for Engineering
• /
• v.1 no.1
• /
• pp.35-43
• /
• 1990

A series of $TiO_2-SiO_2$catalysts were prepared by coprecipitation from the mixed solution of titanium tetrachloride and sodium silicate. Some of the samples were treated with 1N $H_2SO_4$ and used as modified catalysts. The catalytic activities of modified catalysts were higher than those of unmodified catalysts, and the effect of modification on the catalytic activity was higher for 2 - propanol dehydration than for cumene dealkylation. The catalytic activity of unmodified catalysts was correlated with their acid amount for the above two reactions. As $TiO_2-SiO_2$ catalysts had relatively large amount of weak acid sites and small amount of strong acid sites, the catalytic activity for 2 - propanol dehydration was higher than that for cumene dealkylation. The effect of modification on catalytic activity increased with increasing $TiO_2$content of the catalysts. Actually, $92-TiO_2-SiO_2/SO_4{^2}$had the highest increment in catalytic activity and $10-TiO_2-SiO_2/SO_4{^2}$had the lowest increment for the 2 - propanol dehydration.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.8
• /
• pp.2299-2303
• /
• 2010

A new approach to the use of potassium peroxodisulphate as an oxidizing reagent is proposed and applied to the case of oxidative aromatization of 1, 4-dihydropyridines with cetyltrimethylammonium peroxodisulfate, a phase transfer oxidant. We demonstrate how it is possible to increase the reactivity of potassium peroxodisulphate in the presence of phase transfer catalyst. Dealkylation in case of 4-n-alkyl/n-alkenyl was not obtained.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.3
• /
• pp.679-682
• /
• 2009

Utilizing a planar five coordinating N3S2 ligand, 2,6-bis(2-methylthiophenyliminomethyl)pyridine, a pseudo 7-coordinated manganese(II) complex with two labile triflate anions in the axial positions was synthesized. The reaction of the manganese(II) complex with an oxidant, iodosylbenzene, produced a metastable high-valent manganese(IV)-oxo species at 0 ${^{\circ}C}$. The high-valent Mn(IV)-oxo intermediate was characterized with a UV-vis spectrophotometer and an electrospray ionization mass spectroscopy. Reactivity studies of the Mn(IV)=O species revealed that the intermediate is capable of oxygenating $PPh_3$ and N-dealkylating N,N-dimethyl-toludine.

• Korean Journal of Pharmacognosy
• /
• v.39 no.2
• /
• pp.127-134
• /
• 2008

From the under ground part of Aconitum volubile Pall. (Ranunculaceae),seven nor- or di-terpenoid alkaloids were isolated and identified by NMR spectra and mass spectrum. The alkaloids were three $C_{19}$-norditerpenoid alkaloids such as isotalatizidine, altaconitine and vilmorrianine A, and four $C_{20}$-diterpenoid alkaloids such as 12-epidehydronapelline, 12-epinapelline, songoramine and songorine. Some of the isolated diterpenoid alkaloids were subjected to oxidation reaction with active $MnO_2$ and oxoammonium salt. The results were C-12 oxidation(ketone formation) and N-dealkylation in veatchin-type and decomposition to non-alkaloidal compounds in atisine-type ajaconine.

• Archives of Pharmacal Research
• /
• v.26 no.8
• /
• pp.631-637
• /
• 2003

Chloroquine has been used for many decades in the prophylaxis and treatment of malaria. It is metabolized in humans through the N-dealkylation pathway, to desethylchloroquine (DCQ) and bisdesethylchloroquine (BDCQ), by cytochrome P450 (CYP). However, until recently, no data are available on the metabolic pathway of chloroquine. Therefore, the metabolic pathway of chloroquine was evaluated using human liver microsomes and cDNA-expressed CYPs. Chloroquine is mainly metabolized to DCQ, and its Eadie-Hofstee plots were biphasic, indicating the involvement of multiple enzymes, with apparent $K_m and V_{max}$ values of 0.21 mM and 1.02 nmol/min/mg protein 3.43 mM and 10.47 nmol/min/mg protein for high and low affinity components, respectively. Of the cDNA-expressing CYPs examined, CYP1A2, 2C8, 2C19, 2D6 and 3A4/5 exhibited significant DCQ formation. A study using chemical inhibitors showed only quercetin (a CYP2C8 inhibitor) and ketoconazole (a CYP3A4/5 inhibitor) inhibited the DCQ formation. In addition, the DCQ formation significantly correlated with the CYP3A4/5-catalyzed midazolam 1-hydroxylation (r=0.868) and CYP2C8-catalyzed paclitaxel 6$\alpha$-hydroxylation (r = 0.900). In conclusion, the results of the present study demonstrated that CYP2C8 and CYP3A4/5 are the major enzymes responsible for the chloroquine N-deethylation to DCQ in human liver microsomes.

• Journal of Environmental Analysis, Health and Toxicology
• /
• v.21 no.4
• /
• pp.243-251
• /
• 2018

Pharmaceuticals in wastewater effluents have been recognized as emerging pollutants threatening freshwater organisms. To extend understanding for bioaccumulation and toxicity in those organisms, information on biotransformation products (or metabolites) and their metabolic pathway are crucial. The aim of the present study is to identify and elucidate metabolites of pharmaceuticals formed in exposed organisms using suspect and nontarget screening approach using LC-HRMS. As the target pharmaceuticals, carbamazepine, ketoprofen, metoprolol, propranolol, and verapamil were selected whereas Daphnia magna and Gammarus pulex were used as test organisms. After 24h exposure, metabolites formed in the organisms were identified using LC-HRMS. The structures of metabolites were elucidated via analysis of MS/MS fragment pattern and the comparison with fragment database. As the results, a total of 10 metabolites were identified for 5 parent compounds (C253/C356 for carbamazepine, K211 for ketoprofen, M256 for metoprolol, P218/P276/P306 for propranolol, V196/V291/V441 for verapamil). Among them, the presence of C253 and V291 was confirmed using standard materials. Most of the identified metabolites were formed through oxidative reactions such as hydroxylation, N-demethylation, and dealkylation. Cysteine conjugation (phase II reaction) metabolite (C356) for carbamazepine was found in daphnia. The metabolic pathway of verapamil showed similar metabolic pathways and metabolic pathways for both species. Although the toxicological information on the identified metabolites could not be confirmed, the molecular structure information of the proposed metabolites can be used for future evaluation and prediction of toxicity.

• Clean Technology
• /
• v.23 no.2
• /
• pp.196-204
• /
• 2017

CdZnS/ZnO composite was prepared through low-temperature precipitation and drying method. The property of CdZnS/ZnO as a recyclable photocatalyst for the degradation of rhodamine B (RhB) under visible light irradiation was examined. The sample was characterized by XRD, FE-SEM, XPS, UV-vis DRS and photoluminescence techniques before and after repeated reaction to investigate the change of properties during the photocatalytic reaction. During repeated reaction, the CdZnS/ZnO showed an improved photocatalytic activity and recycle stability. Among two feasible reaction pathways for photocatalytic degradation of RhB, the cleavage of conjugated chromophore was found to predominate over N-dealkylation of chromophore skeleton in the present work. The results indicate that the CdZnS/ZnO, prepared by a simple precipitation method, can be used as a visible-light driven photocatalyst with enhanced cycle stability and activity.