• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3690-3694
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• 2013

The $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) is a new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet state Cl2Ge=Ge: and formaldehyde has been investigated with CCSD(T)//MP2/$6-31G^*$ method. From the potential energy profile, it could be predicted that the reaction has only one dominant reaction pathway. The reaction rule presented is that the two reactants first form a fourmembered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the ${\pi}$ orbital of formaldehyde forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge: atom in intermediate hybridizes to an $sp^3$ hybrid orbital after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between $H_2Ge=Ge:$ and formaldehyde, and laid the theory foundation of the cycloaddition reaction between $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) and asymmetric ${\pi}$-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds. The study extends research area and enriches the research content of germylene chemistry.

• Journal of Photoscience
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• v.7 no.2
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• pp.67-71
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• 2000

A quantum-chemical investigation on the conformations and electronic properties of trans(diphenyl-diheterocyclic) ethenes(t-PHEs) as building block for fully $\pi$-conjuated polymer are performed in order to display the effects of heterocyclic ring substitution. Structures for the molecules, t-PHEs were fully optimized by using semiempirical AM1, PM3 methods, and ab initio HF methods, with 6-31G basic set. The potential energy curves with respect to the change of single are obtained by using ab initio HF/6-31G basic set. The curves are not similar shapes in the molecules with respect to heterocyclic rings. It is shown that the steric repulsion interactions between phenyl ring and heterocyclic ring are subjected to different type with the respect to each heterocyclic ring. Electronic properties of the molecules were molecules were obtained by applying the optimized structures and selected geometries to the extended Huckel method. To investigate the change of HOMO-LUMO gap with respedt to the torsion angle, we select the optimized structures. By using the results, the dependency of conjugation for the energy gaps is analyzed. For t-PHE the energy gap increase up to 0.52 eV compared with its planar structure. In the cases of t-PHE and t-PHE, the energy gap increase by 1.29 and 1.15 eV, respectively, compared with its planar structure.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4079-4083
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• 2012

The mechanism of the cycloaddition reaction between singlet state dichlorosilylene germylidene ($Cl_2Si=Ge:$) and acetone has been investigated with B3LYP/6-$31G^*$ and B3LYP/6-$31G^{**}$ method, from the potential energy profile, we predict that the reaction has one dominant reaction pathway. The presented rule of the reaction is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the Si-heterocyclic four-membered ring germylene and the ${\pi}$ orbital of acetone forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the Si-heterocyclic four-membered ring germylene further combines with acetone to form an intermediate. Because the Ge atom in the intermediate hybridizes to an $sp^3$ hybrid orbital after the transition state, then, the intermediate isomerizes to spiro-heterocyclic ring compound involving Si and Ge (P4) via a transition state.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2585-2591
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• 2012

A series of heterocyclic chalcone derivatives bearing heterocycles such as thiophene or furan ring as an isostere of benzene ring were carefully prepared, and the influence of heterocycles on 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activities was systematically investigated. Structure-activity relationships (SAR) analysis showed that the activities of thiophene ring-containing chalcones were higher than those of furan ring-containing chalcones, and the presence of methyl substituent of heterocyclic ring distinctly affected the activities compared with non-substituted heterocycles in an opposite manner, with the 4'-methyl group of thiophene ring increasing activity and the 3'-methyl group of the furan ring decreasing activity. The distinct isosteric effect of heterocycles (i.e., thiophene or furan ring) on radical scavenging activities of heterocyclic chalones was distinctly demonstrated in our work.

• Food Science and Biotechnology
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• v.17 no.5
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• pp.1032-1037
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• 2008

Lowly volatile heterocyclic sulfur compounds generated in autoclaved garlic extract were isolated and identified, and their antimicrobial activity was determined. Two kinds of unusual volatile sulfur compounds were separated from heated garlic by preparative recycling high performance liquid chromatography (HPLC), and identified by gas chromatography (GC)-mass spectrometry (MS) and $^1H$-nuclear magnetic resonance (NMR). They had heterocyclic structures with 4 to 5 sulfur atoms in the molecules. 4-Methyl-1,2,3-trithiolane (MTTT) is highly volatile and was not able to be concentrated, and was identified by GCMS only. MTTT and 6-methyl-1,2,3,4,5-pentathiepane (MPTP) are lowly volatile and were obtained in pure states to be positively identified for the first time. All 3 heterocyclic sulfur compounds began to appear by the time when the early-formed diallyl sulfides started to disappear. The minimum inhibitory concentration range of MTTT and MPTP was determined to be between 1 and 6 ppm against all yeasts tested. MTTT and MPTP were lowly volatile and sparingly soluble in water.

• Journal of the Korean Chemical Society
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• v.57 no.3
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• pp.361-364
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• 2013

A modified synthetic approach to the synthesis of heterocyclic food mutagens, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PHIP) and 2-amino-1,6-dimethylimidazo[4,5-b]pyridine (DMIP) is reported. This route highlights an optimized palladium catalysed Buchwald cross-coupling of 2-halo-1-methyl-imidazo[4,5-b]pyridine with benzophenoneimine followed by acidic hydrolysis to yield compound 7. Using finely tailored conditions, Suzuki cross-coupling reactions with highly efficient catalytic systems were performed as the final step on 8 to introduce the aryl group and methyl group on the heterocyclic core.

• Bulletin of the Korean Chemical Society
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• v.1 no.2
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• pp.54-57
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• 1980

Trichloromethylphosphonyl dichloride was prepared by the aluminium chloride method. We synthesized several heterocyclic compounds containing phosphorus atom by the stepwise esterification of trichloromethylphosphonyl dichloride with ethylene glycol, 2-mercaptoethanol, ethylene diamine, and 2-aminoethanol and the resulting heterocyclic compounds are 2-trichloromethyl-1,3,2-dioxa-, 2-trichloromethyl-1,3,2-thioxa-, 2-trichloromethyl-1,3,2-diaza-, 2-trichloromethyl-1,3,2-diaza-, and 2-trichloromethyl-1,3,2-oxazaphospholane-2-oxide. The best results were obtained in the solution of triethylamine as hydrochloric acid trapping agent. The structure of five-membered heterocyclic phosphonates were characterized by their IR, NMR, and elementary analysis and the mass spectra of the compounds were analyzed.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.789-791
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• 2002

• Bulletin of the Korean Chemical Society
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• v.33 no.4
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• pp.1375-1378
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• 2012

• Journal of Food Hygiene and Safety
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• v.14 no.4
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• pp.386-396
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• 1999

Commonly eaten fish, meat and other protein-containing foods show some level of mutagenic activity following normal cooking such as broiling, frying, grilling, roasting etc. The main food mutagens found in cooked products are“heterocyclic aromatic amines”. Several of them have been shown to be carcinogenic in rodent and suggested to be relevant for human cancer etiology. This review summarizes the chemistry, formation, occurrence and toxicity of food-borne heterocyclic aromatic amines. Factors that influence the formation of them are also discussed with special emphasis on dietary factors. From a health safety point of view, it is desirable to estimate the intake of heterocyclic amines via foods, and reduce or prevent the formation of food mutagens.