• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.174-178
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• 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.

• 공업화학
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• 제1권1호
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• pp.35-43
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• 1990

일련의 $TiO_2-SiO_2$촉매를 $TiCl_4$와 $Na_2SiO_3$혼합용액을 공침전시켜 제조하였으며 이중 일부의 촉매는 1N $H_2SO_4$로 처리하여 촉매표면을 개질하였다. 개질된 촉매의 촉매활성은 개질 안된 촉매보다 높은 촉매활성을 나타내었으며 cumene dealkylation 반응에서 보다 2 - propanol dehydration 반응에서 더욱 효과가 크게 나타났다. 개질 안된 촉매의 상기 두 반응에 대한 촉매활성은 산의 양과 관계가 있었다. $TiO_2-SiO_2$촉매는 비교적 많은 양의 약한 산자리와 작은 양의 강한 산자리를 가졌기 때문에 cumene dealkylation 반응에서 보다 2 - propanol dealkylation 반응에 더 높은 촉매활성을 나타내었다. 촉매활성에 미치는 $H_2SO_4$의 개질효과는 $TiO_2$ 함량에 비례하였으며 $92-TiO_2-SiO_2/SO_4^2$가 2 - propanol dealkylation 반응에 가장 큰 촉매활성의 증가를 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2299-2303
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• 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
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• 제30권3호
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• pp.679-682
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• 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.

• 생약학회지
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• 제39권2호
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• pp.127-134
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• 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
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• 제26권8호
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• pp.631-637
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• 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.

• 환경분석과 독성보건
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• 제21권4호
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• pp.243-251
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• 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.

• 청정기술
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• 제23권2호
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• pp.196-204
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• 2017

CdZnS/ZnO 복합체를 저온에서의 침전 및 건조 과정을 거쳐 제조한 다음, 가시광선 조사하에서 로다민 B 염료의 광분해에 대한 광촉매로서의 활성 특히 광촉매 재활용 특성에 대해 중점을 두고 고찰하였다. 광반응 과정에서의 광촉매 변화를 조사하기 위해 X선 회절분석기, 전계방사형 주사전자현미경, X-선 광전자 분광법, UV-vis 확산반사 분광법 그리고 광자발광 분광기 등을 이용하여 반응 전후의 광촉매 시료에 대해 물성분석을 행하였다. 계속적으로 반복되는 반응을 통하여 CdZnS/ZnO 광촉매는 보다 향상되고 안정된 활성을 나타냄을 볼 수 있었다. 로다민 B의 광분해반응에 대해 가능한 두 가지의 반응기구 중에서도 본 연구에서는 발색단 골격의 탈알킬화 반응보다는 발색단 콘쥬케이트 구조의 절단 과정을 거쳐 주로 반응이 진행되는 것으로 확인되었다. 이러한 결과들로부터 단순 침전법으로 용이하게 제조할 수 있는 CdZnS/ZnO는 비교적 높은 활성과 재활용성을 지닌 가시광선용 광촉매로 사용 가능하다는 것을 알 수 있었다.