• YAKHAK HOEJI
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• v.40 no.3
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• pp.300-305
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• 1996

The base-induced elimination of N-protected 2-(bromomethyl)pyrrolidines 12a-c with KHMDS in THF at -78$^{\circ}C$ for 1h gave exocyclic enamines 13a-c. The acidic catalyzed pr otonation on ${\beta}$-carbon atom of 2-(methylene)pyrrolidines 13a-c with $H_3PO_4$ formed endocyclic N-iminium intermediates 14(or 15). Nucleophilic attack of alpha-carbon atom and hydrolysis of N-iminium ion gave carbocationic adduct (aminoalcohol) 16 from which 5-amino-2-pentanones 17a-c were formed after deprotonation.

• Clean Technology
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• v.16 no.4
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• pp.239-244
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• 2010

The carboxylation of the fluorenyl epoxide with a spiro framework, 9,9'-Bis(4-oxiranylmethoxyphenyl) fluorine (2) was catalyzed by some onium salts such as quaternary ammonium and phosphonium salts to produce the corresponding five-membered cyclic carbonate (3) in an efficient and environmentally benign fashion. The coupling reactions depend greatly on the kind of the halide anions and alkyl chain length of the onium salts. While the reaction was sensitive to the reaction temperature, the reaction trends suggest that the catalytic efficiency of the quaternary ammonium halides may correlate strongly with the melting points of the halides. The reactions using a catalytic amount (2 mol %) of quaternary ammonium bromide with an n-butyl chain at 75.9 bar of $CO_2$ and 393 K give the highest yield of the cyclic carbonate (92%).

• Journal of the Korean Chemical Society
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• v.33 no.5
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• pp.545-550
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• 1989

When (3R,4R)-1-(1-benzyloxycarbonyl-2-methyl-1-propenyl)-4-mercapto-3-phenylacetamidoazetidin-2-one(8) was reacted with carbon disulfide and alkyl halides in the presence of triethylamine, the ${\beta}$-lactam ring was cleaved to give (Z)-and (E)-1-alkylthio-5-benzyloxycarbonyl-6-methyl-2-phenylacetamido-4-aza-1,5-heptadien-3-one (13-16) or 2-benzyl-4-(3-benzyloxycarbonyl-4-methyl-1-oxo-2-aza-3-pentenyl)thiazole(17).

• Bulletin of the Korean Chemical Society
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• v.16 no.5
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• pp.416-421
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• 1995

The approximate rates and stoichiometry of the reaction of excess lithium gallium hydride with selected organic compounds containing representative functional groups were examined under the standard conditions (diethyl ether, 0 $^{\circ}C)$ in order to compare its reducing characteristics with lithium aluminum hydride and lithium borohydride previously reported, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, and amines evolve hydrogen rapidly and quantitatively. However lithium gallium hydride reacts with only one active hydrogen of primary amine. Aldehydes and ketones of diverse structure are rapidly reduced to the corresponding alcohols. Conjugated aldehyde and ketone such as cinnamaldehyde and methyl vinyl ketone are rapidly reduced to the corresponding saturated alcohols. p-Benzoquinone is mainly reduces to hydroquinone. Caproic acid and benzoic acid liberate hydrogen rapidly and quantitatively, but reduction proceeds slowly. The acid chlorides and esters tested are all rapidly reduced to the corresponding alcohols. Alkyl halides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced slowly. Benzonitrile consumes 2.0 equiv of hydride rapidly, whereas capronitrile is reduced slowly. Nitro compounds consumed 2.9 equiv of hydride, of which 1.9 equiv is for reduction, whereas azobenzene, and azoxybenzene are inert toward this reagent. Cyclohexanone oxime is reduced consuming 2.0 equiv of hydride for reduction at a moderate rate. Pyridine is inert toward this reagent. Disulfides and sulfoxides are reduced slowly, whereas sulfide, sulfone, and sulfonate are inert under these reaction conditions. Sulfonic acid evolves 1 equiv of hydrogen instantly, but reduction is not proceeded.

• Korean Chemical Engineering Research
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• v.48 no.3
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• pp.332-336
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• 2010

Ionic liquid immobilized on mesoporous amorphous silica was prepared from the coupling of 1-(triethoxysilylpropyl)-3-n-alkyl-imidzolium halides with tetraethyl orthosilicate(TEOS) through template-free condensation under strong acidic conditions. The immobilized 1-n-butyl-3-methyl imidazolium bromide ionic liquid on amorphous silica(BMImBr-AS) was proved to be an effective heterogeneous catalyst for the synthesis of dimethyl carbonate(DMC) from transesterification of ethylene carbonate(EC) with methanol. High temperature, high carbon dioxide pressure and long reaction time were favorable for the reactivity of BMImBr-AS. Kinetic studies based on two step reactions revealed that the proposed reaction model fitted well the experimental data. The apparent activation energy was estimated to be 67.4 kJ/mol.

• Journal of the Korean Chemical Society
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• v.47 no.2
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• pp.137-146
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• 2003

3-Hydroxybenzopyran[3,2-c]-[1]-benzopyran-6,7-diones (3) and 3-methoxycarbonylcoumarin (4) were prepared via condensation of 1 with resorcinol in the presence of sodium methoxide. The chemical behavior of 3 towards acetic anhydride, alkyl halides and diazonium chloride is described. The electron impact ionization mass spectra of compounds 4,5 and 6a,b show a weak molecular ion peak and a base peak of m/z 89, m/z 280. m/z 91 and m/z 120 resulting from a cleavage fragmentation respectively. The molecular ion of compounds 3, 6b, and 7a is a base peak of m/z 280, m/z 366 and m/z 488 respectively. Compound 7a give a characteristic fragmentation pattern with a two very stable fragmentation of m/z 383 and m/z 77.

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2962-2968
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• 2009

The photodissociation dynamics of 1,2-bromochloroethane ($C_2H_4BrCl$) was investigated near 234 nm. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br($^2P_{3/2}$) and Br${\ast}($^2P_{1/2}$) atoms. The total translational energy distributions for the Br and Br${\ast}$ channels were well characterized by Gaussian functions with average translational energies of 100 and 84 kJ/mol, respectively. The recoil anisotropies for the Br and Br${\ast}$ channels were measured to be ${\beta}$ = 0.49 ${\pm}$ 0.05 for Br and 1.55 ${\pm}$ 0.05 for Br${\ast}$. The relative quantum yield for Br${\ast}$ was found to be ${\Phi}_{Br{\ast}}$ = 0.33 ${\pm}$ 0.03. The probability of nonadiabatic transition between A' states was estimated to be 0.46. The relevant nonadiabatic dynamics is discussed in terms of interaction between potential energy surfaces in Cs symmetry.

• Journal of the Korean Chemical Society
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• v.39 no.7
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• pp.564-571
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• 1995

5-Amino-2H-1,2,4-thiadiazoline-3-one has been prepared from 2-thiobiuret through a oxidative cyclization under basic hydrogen peroxide condition. Lactam-lactim tautomerism of 5-amino-2H-1,2,4-thiadiazoline-3-one has been examined by spectroscopic methods and ab initio molecular orbital calculation. These results were shown that 5-amino-2H-1,2,4-thiadiazoline-3-one exists as lactam form. Reaction conditions for alkylating 5-amino-2H-1,2,4-thiadiazoline-3-one with alkyl halides in the presence of various bases were studied in DMF and $H_2O$-THF two phase system. $Li_2CO_3$ base in DMF method gave best result in this investigation. The alkylation has been taken place at N-2 position. The identification of the product is confirmed by spectral data of IR, $^1H$ NMR and $^13C$ NMR and the comparison of authentic sample, 5-amino-2-methyl-1,2,4-thiadiazolidine-3-one, obtained from the oxidative cyclization of 5-methyl-2-thiobiuret.