• Applied Chemistry for Engineering
• /
• v.26 no.3
• /
• pp.366-371
• /
• 2015

The kinetic behavior of tetrahydrotricyclopentadiene (THTCPD) isomerization was studied by using two kinds of chloroaluminate ionic liquid (IL) catalyst with different Lewis acidity. THTCPD isomerization pathway was discussed under the different temperature and time as reaction parameters using IL catalysts consisting of 1-butyl-3-methylimidazolun chloride $(BMIC)/AlCl_3$ with low acidity and pyridine hydrochloride $(PHC)/AlCl_3$ with high acidity. The conversion of THTCPD isomerization increased with increasing Lewis acidity of IL catalyst. The THTCPD isomerization pathway changed as a function of reaction temperature and catalyst acidity. In the case of $BMIC/AlCl_3$ IL catalyst, THTCPD isomerization pathway was similar to that of using conventional $AlCl_3$ catalyst. However, two different types of additional pathways (endo, exo, endo-NB ${\rightarrow}$ exo, exo, endo-NB ${\rightarrow}$ exo, exo, exo-NB and endo, exo, endo-NB ${\rightarrow}$ exo, exo, endo-NB ${\rightarrow}$ exo, exo, exo-CP) were appeared when using $PHC/AlCl_3$ IL catalyst.

• Applied Chemistry for Engineering
• /
• v.18 no.1
• /
• pp.36-40
• /
• 2007

The study on the isomerization reaction of endo-tetrahydrodicyclopentadiene and endo-tetrahydrodi(methylcyclopentadiene) using heteropolyacid catalyst was carried out. Exo compound was prepared from endo compound through isomerization reaction. To improve the problem of aluminum chloride as an isomerization catalyst, application of heteropolyacid was attempted. In use of Keggin type heteropolyacid, catalytic activity was extremely high at cesium substitution instead of 2.5 hydrogen atoms of $H_3PW_{12}O_{40}$. Using the cesium substituted heteropolyacid, isomerization reaction rate was faster than aluminum chloride and the effect of reaction temperature and times on reactivities were compared in isomerization of tetrahydrodicyclopentadiene and tetrahydrodi(methylcyclopentadiene).

• Korean Chemical Engineering Research
• /
• v.43 no.5
• /
• pp.566-570
• /
• 2005

The study on the hydrogenation and isomerization of unsaturated bicyclic hydrcarbon compounds using methylcyclopentadiene dimer (MCPD) was carried out. Exo compound was prepared through isomerization reaction after two hydrogenation reaction steps. In the first hydrogenation reaction which needs one mole of hydrogen, the formation rate of monomer was increased as dimer was decomposed at reaction temperature above $100^{\circ}C$. At first hydrogenation, DHDMCPD [dihydrodi(methylcyclopentadiene)] was formed and second hydrogenation was proceeded to produce THDMCPD [tetrahydrodi(methylcyclopentadiene)], the ratio of exo to endo THDMCPD was varied by the control of 2nd hydrogenation temperature. To improve the process, continuous 1st and 2nd hydrogenation conditions were established by using the 2nd stage heat controllable reactor. Also, catalytic activities were compared by the use of halogenized aluminum, metal halides and solid acids catalysts on the isomerization reaction from endo to exo THDMCPD.

• Proceedings of the Korean Society of Propulsion Engineers Conference
• /
• 2006.05a
• /
• pp.193-196
• /
• 2006

This paper presents the results of catalytic endo- to exo- isomerization of saturated poly cyclic compound. Several zeolites were tested and influences of, Si/Al ratio and Structures of the zeolites on the reaction were investigated. The results showed that Y zeolites were more active than other zeolites, because of its large pore size and relative strong acidity. In all Y zeolites with different Si/Al, Y-5.4 is best. In all the zeolites tested, Y calcined at $450^{\circ}C$ was favorable. Still now the aluminium chloride catalyst is more active than zeolites. However, considering of environmental problems, corrosion, and treatment can make the zeolite catalyst substitute the aluminium chloride catalyst.

• Applied Chemistry for Engineering
• /
• v.25 no.1
• /
• pp.66-71
• /
• 2014

Synthesis of exo-tetrahydrodicyclopentadiene (exo-THDCPD) through the isomerization of endo-tetrahydrodicyclopentadiene (endo-THDCPD) was investigated over HY zeolite catalysts. Conversion of endo-THDCPD increased with the increase of $Si/Al_2$ ratio of HY zeolite catalysts, which can be attributed to increase of acid strength with increase of $Si/Al_2$ ratio. Yield of exo-THDCPD, however, was the highest over HY with $Si/Al_2$ ratio of 30, because the production of cyclopentadiene and oligomers was minimized. The optimal reaction temperature was $180^{\circ}C$ because the higher reaction temperature increased the production of by-products. The yield of exo-THDCPD also increased with the amount of the catalyst in feed. In the isomerization reaction of endo-THDCPD using the HY zeolite catalysts, it was confirmed that the internal diffusion resistance in the pore of catalysts would have more significant effects on the reaction activity than that of the external diffusion resistance of catalysts.

• Bulletin of the Korean Chemical Society
• /
• v.28 no.12
• /
• pp.2153-2161
• /
• 2007

The transition metal-induced in situ generation of carbene complexes from alkynes having a carbonyl or imino group as a nucleophilic functionality has been investigated. These reactive carbenoid species are generated with high atom efficiency through a 6-endo-dig cyclization mode based on the electrocyclization of vinylidene complexes or a 5-exo-dig cyclization mode in π-alkyne complexes, and have been found to serve as versatile intermediates in catalytic carbene transfer reactions. Highlighted and reviewed in this account are the generation and preparation of pyranylidene, furylcarbene, pyrrolylcarbene, and vinylcarbene complexes and their application to [3,3]sigmatropic rearrangement of acylcyclopropylvinylidenes, catalytic cyclopropanation reactions, [2,3]sigmatropic rearrangement or condensation reactions via ylides, ring-opening and substitution reactions with heteroaromatic compounds, and catalytic isomerization of oligoynes.

• Applied Biological Chemistry
• /
• v.26 no.4
• /
• pp.222-230
• /
• 1983

This study was designed to develop a process for the immobilization of xylose isomerase(D-xylose ketol isomerase, EC 5.3.1.5) from Streptomyces griseolus previously isolated by the authors and its application on a pilot plant scale for the production of high fructose corn syrup. The biomass which has endo-excreted xylose isomerase was homogenized under a pressure of $500kg/cm^2$ and 90.8% of the enzyme recovery of the native activity was obtained as compared to 54.7% recovery by the lysozyme treatment. Ionic bonding method was adopted for the enzyme immobilization due to its many reported merits. It was found that the porous resins such as Diaion HP 20, Duolite A-7, Amberlite IRA 93 and 94 were effective in immobilizing the enzyme. In addition, it was disclosed that the regeneration form of $BO_4--$ is effective for Amberlite IRA 93 and $HCO_3-$ for Diaion HP 20. Optimal immobilization condition for Amberlite IRA 93 was pH 8.0 and $55^{\circ}C$ yielding 80.6% of immobilization. Activity decay test showed half life of the immobilized enzyme with Amberlite IRA 93 was more than 24 days at $65^{\circ}C$. The carrier was evaluated to be resuable and its result showed the relative immobilization yields were 98.2, 93.3, 90.7 and 87.5%, respectively at second, third, forth and fifth rebinding test of the enzyme on Amberlite IRA 93. Optimal temperature of the immobilized enzyme was slightly lowered and the range widened to $60\sim70^{\circ}C$, while optimal pH moved toward $8.0\sim8.3$ in its isomerization reaction. The trial production result of high fructose corn syrup in pilot scale immobilization showed that one liter of immobilized xylose isomerase (350 IXIU/ml-R) is capable producing about 293l high fructose corn syrup(75% dry substance) in 30 days.