• Applied Chemistry for Engineering
• /
• v.2 no.4
• /
• pp.411-420
• /
• 1991

The dehydrocyclization of n-heptane was studied over $Pt-Sn/{\gamma}-Al/_2O_3$ catalysts with varying Sn content in a fixed bed continuous flow reactor. The range of experimental conditions was at the temperature between 450 and $550^{\circ}C$, the pressure $20{\times}10^5-50{\times}10^5Pa$, the contact time 0.09 and 0.27 hr and the $H_2/H.C$. mole ratio 10. The conversion and selectivity of dehydrocyclization increased with increasing temperature, but decreased with increasing pressure. When we use Sn as a promoter, the selectivity of dehydrocyclization changesa a little, but the conversion was increased and the selectivity of isomerization increased a lot. The activation energy of dehydrocyclization of n-heptane was 34.5 kcal/mol over 0.6 wt % Pt-0.6 wt % $Sn/{\gamma}-Al_2O_3$.

• Journal of the Korean Chemical Society
• /
• v.49 no.4
• /
• pp.426-430
• /
• 2005

• Journal of the Korean Chemical Society
• /
• v.20 no.2
• /
• pp.136-140
• /
• 1976

The photocyclodehydrogenation reaction of o-terphenyl type compounds has been interpreted with perturbational molecular orbital theory. Results show that the mobile bond order for the first excited state is a good reactivity index and this approach is also consistent with the orbital symmetry conservation rule of Woodward and Hoffmann.

• KSBB Journal
• /
• v.18 no.3
• /
• pp.222-228
• /
• 2003

This study was performed to research a chemo-enzymatic synthesis of sorbitan acrylate. It w as firstly to determine the optimum conditions for D-sorbitol cyclic reaction in the presence of p-toluenesulfonic acid (p-TSA) as catalyst material. It was secondly to find the optimum conditions for sorbitan acrylate synthesis using immobilized lipase Novozym 435 in t-butanol from its materials. The maximum yield of 1,4-sorbitan synthesis were obtained approximately 90% (w/w) at 13$0^{\circ}C$ and 200 mmHg vacuum pressure with 1% (w/w) p-TSA after 150 min reactin time on our experimental system. The product from optimum condition was less color than those obtained at higher temperatures and minimized byproduct and unreacted D-sorbitol. Sorbitan acrylate was synthesized to around 63.5% conversion of 1,4-sorbitan. The experimental optimum condition was found at 5$0^{\circ}C$, atmospheric pressure, 3% (w/v) Novozym 435, 50 g/L 1,4-sorbitan of initial reactant concentration, and 1:3 molar ratio of 1,4-sorbitan to acrylic acid.

• Journal of the Korean Chemical Society
• /
• v.28 no.6
• /
• pp.384-392
• /
• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

• Textile Coloration and Finishing
• /
• v.7 no.4
• /
• pp.39-44
• /
• 1995

A study has been made about some correlations in the chemical cyclization of precursors, poly(ether-amide-amic acid)s by treating in solution a mixture of acetic anhydride and pyridine in the presence of 4,4-dimethyl formamide, with the poly(ether-amic acid)s being respectively reacted between trimellitic anhydride chloride and 3 kinds of diamines, i.e., 4,4'-bis(m-aminophenoxy) benzophenone, 2,2'-bis[4-(m-aminophenoxy) phenyl] propane and 4,4'-bis(m-aminophenoxy) diphenyl sulfone. The cyclization of imide ring in the poly(ether-amide-amic acid)s may be regarded as an intramolecular acylation of amide group by o-carboxyl group. As a result of this reseach, the effects on the conversion to poly(ether-amide-imide)s have been found by changing the ratio of cosolvents in the cyclization mixture.

• Journal of the Korean Chemical Society
• /
• v.55 no.2
• /
• pp.230-234
• /
• 2011

The present study describes the synthesis of 4,5-dihydro-6-(4-methoxy-3-methylphenyl)-3(2H)-pyridazinone derivatives. The synthesis of the first target compound, 4,5-dihydro-6-(4-methoxy-3-methylphenyl)-3(2H)-pyridazinone (1), was achieved by Friedel-Crafts acylation of o-cresyl methyl ether with succinic anhydride and subsequent cyclization of the intermediary g-keto acid with hydrazine hydrate. Condensation of compound 1 with aromatic aldehydes in the presence of sodium ethoxide affords the corresponding 4-substituted benzyl pyridazinones (3a-d). The dihydropyridazinone 1 underwent dehydrogenation upon treatment with bromine/acetic acid mixture to give (4). Pyridazine (5) has been synthesized upon the reaction of pyridazinone (1) with 1,3-diphenyl-2-propen-1-one under the Michael addition reaction. N-dialkylaminomethyl derivatives 6a-b have been obtained from the reaction of pyridazinone 1 with formaldehyde and secondary amine, whereas reaction of 1 with formaldehyde gives N-hydroxymethyl derivative (7). This study also includes the synthesis of the 3-chloropyridazine derivative 8 in excellent yield by heating pyridazinone 3b in phosphorus oxychloride. The behaviour of the chloro derivative toward sodium azide, benzyl amine and anthranilic acid was also studied. The proposed structures of the products were confirmed by elemental analysis, spectral data and chemical evidence.

• Polymer(Korea)
• /
• v.26 no.4
• /
• pp.439-444
• /
• 2002

Several monomeric benzilidene anhydrides (2a~d) haying n-alkyloxy groups with various n-alkyl chain lengths were prepared by Stobbe condensation of diethyl succinate with 4-(n-alkyloxy)benzaldehyde (1a,b) followed by hydrolysis by the succinates and cyclodehydration of the benzilidenated succinic acids. Configurational isomerism of the monomer was investigated by spectroscopic means. It was found that monomers (2a~d) exist in (Z,Z)-isomeric structure. Polymerization was carried out in bulk at 150~$210^{\circ}C$ range in nitrogen flow. The chemical structure and thermal properties of the polymers were characterized by spectroscopic means, TGA and DSC. Their properties highly depended on their chemical structures in accordance with a side chain length.

• Applied Chemistry for Engineering
• /
• v.17 no.2
• /
• pp.177-182
• /
• 2006

In this work, we have prepared organophilic MMT having thermal stability by ion exchange reaction of various aromatic ammonium salts with MMT containing sodium ion. The organic modifiers having alkyl side chains and amine functional group were successfully synthesized by effectively introducing the surfaces of MMT via ion exchange reaction to form organophilic MMTs with a view to improve the reactivity and thermal stability. The WAXD patterns of organophilic MMT showed the more increased gallery spacing by $3.3{\AA}$ than that of the pristine MMT and also the onset of initial decomposition of organophilic MMT was $275^{\circ}C$ as determined by a thermogravimetric analysis. The polyimide (PI) nanocomposite films based on poly(amic acid) and organophilic MMT were prepared by a solution blending followed by cyclodehydration reaction. We have investigated the dispersity of organophilic MMTs in PI matrix by using WAXD and the effect of the organophilic MMT content on the mechanical properties of PI nanocomposite films was studied.

• Journal of the Korean Chemical Society
• /
• v.55 no.4
• /
• pp.612-619
• /
• 2011

Lanthanide(III) complexes of 1,2-diphenyl-4-butyl-3,5-pyrazolidinedione(phenylbutazone, PB) have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, UV-Vis. and NMR spectra. The spectral data reveal that the PB acts as a bidentate and mono-ionic ligand coordinating through both the carbonyl oxygens of the pyrazolidinedione ring. The molar conductance data suggest that the complexes are non-electrolytes. The thermal behaviour of the complexes was studied by TG and DTG in air atmosphere and the results provide information about dehydration, thermal stability and thermal decomposition. The final products are found to be the corresponding metal oxides. The thermodynamic parameters and kinetic parameters were evaluated for the dehydration and decomposition stages. The negative entropy values of the decomposition stages indicate that the activated complexes have a more ordered structure than the reactants and that the reactions are slower than normal. Based on these studies, the complexes have been formulated as $[Ln(PB)_3]{\cdot}5H_2O$(Ln=La and Ce) and $[Ln(PB)_3(H_2O)_2]{\cdot}2H_2O$(Ln=Pr, Nd and Sm).