• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3565-3569
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• 2013

A home-made pinhole-type glass nozzle was employed to generate vibronically excited but jet-cooled benzyl-type radicals from precursor 2-fluoro-4-chlorotoluene with a large amount of carrier gas He, from which the visible vibronic emission spectrum was recorded with a long-path monochromator. From an analysis of the spectrum observed, it was found that two benzyl-type radicals, 2-fluorobenzyl and 2-fluoro-4-chlorobenzyl radicals, were formed from the precursor in corona discharge. The possible pathway for the production of benzyl-type radicals that can explain the spectroscopic observation is herein proposed. In addition, the electronic energy of the $D_1{\rightarrow}D_0$ transition and the vibrational mode frequencies in the $D_0$ state of the 2-fluoro-4-chlorobenzyl radical were determined for the first time.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2479-2482
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• 2010

Using a pinhole-type glass nozzle equipped for a corona-excited supersonic expansion (CESE), precursor 2,6-dichlorotoluene seeded in a large amount of inert carrier gas helium was discharged to produce jet-cooled but electronically excited benzyl-type radicals. The visible vibronic emission spectrum was recorded with a long-path monochromator to observe vibronic bands in the $D_1{\rightarrow}D_0$ electronic transition of benzyl-type radicals. The spectral analysis revealed the generation of not only the 2,6-dichlorobenzyl radical as a typical product, but also the o-chlorobenzyl radical as an unexpected species, which indicates the possible molecular rearrangement in eliminating a chlorine atom from the benzene ring. A possible mechanism is proposed for the formation of the o-chlorobenzyl radical from the precurs or in the gas phase.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.1993-1995
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• 2007

A substitution effect on the electronic transition of bi-substituted benzyl-type radicals was discovered. The origin of the electronic D1 → D0 transition of benzyl-type radicals was red-shifted upon substitution to the benzene ring. For symmetric bi-substituted benzyl-type radicals, it was found that the predicted shift obtained from mono-substituted benzyl-type radicals agreed well with the observation. The reason for this agreement is believed that the substituent contributes independently to the electronic energy. The substitution effect was applied to the symmetric bi-substituted difluoro-, dichloro- and dimethylbenzyl radicals.

• Journal of the Korean Chemical Society
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• v.55 no.5
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• pp.741-745
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• 2011

Well-resolved vibronic emission spectra were recorded in the visible region from the corona discharge of precursor alkylbenzenes in a technique of corona excited supersonic expansion using a pinhole-type glass nozzle. From the observed spectra, we found the evidence of the presence of benzyl-type radicals generated by dissociation of C-C or C-H bonds of alkyl group. After identification of benzyl-type radicals formed in the corona discharge, we suggest that energy densities in alkyl chain play a crucial role in determining the bond dissociation during corona excitation.

• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1459-1460
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• 2004

• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.2783-2785
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• 2010

Searching for new molecular radicals which are believed to play an important role as reaction intermediates in aromatic chain reactions, we have applied the technique of corona excited supersonic expansion employing a pinhole-type glass nozzle to obtain the vibronic spectrum from the corona discharge of precursor 3,5-difluorotoluene with a large amount of inert carrier gas helium. An analysis of the observed spectrum revealed that many vibronic bands are from other isomeric difluorobenzyl radicals generated in the jet by migration of the fluorine atom or methylene group to the adjacent position in the 3,5-difluorobenzyl radical. A possible mechanism was proposed for the formation of other isomers by using a bridged cyclic intermediate structure.

• Proceedings of the Korean Society of Propulsion Engineers Conference
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• 2010.11a
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• pp.294-299
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• 2010

Thermal stability of exo-tetrahydrodicyclopentadiene (exo-THDCP) were investigated in a batch-type reactor perfectly coated with quartz. The 1 ml liquid product, which was a sufficiently small amount so as not to affect the reaction pressure, was sampled at 90 min intervals during the reaction and determined by gas chromatography-mass spectrometry (GC-MS) to measure thermal decomposition products of exo-THDCP and specify mechanism for additives (thermal stabilizer). Hydrogen donors (thermal stabilizer) such as 1,2,3,4-tetrahydroquinoline (THQ), benzyl alcohol (BnOH) increased thermal stability of exo-THDCP. These materials donated hydrogen to radical of exo-THDCP produced after initiation of exo-THDCP to decrease activity of primary products of exo-THDCP.

• Clean Technology
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• v.26 no.3
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• pp.204-210
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• 2020

In this study, the ignition characteristics of bio jet fuel (Bio-7629, Bio-5172) produced by F-T process and petroleum-based jet fuel (Jet A-1) were compared and analyzed. The ignition delay time of each fuel was measured by means of a combustion research unit (CRU) and the results were explained through an analysis of the properties and composition of the fuel. The ignition delay time of Bio-5172 was the shortest while that of Jet A-1 was the longest because Jet A-1 had the highest surface tension and Bio-5172 had the lowest viscosity in terms of fuel properties that could affect the physical ignition delay time. As a result of the analysis of the constituents' type and ratio, 22.8% aromatic compounds in Jet A-1 could generate benzyl radical, which had low reactivity during the oxidation reaction, affecting the increase of ignition delay time. Both Bio-7629 and Bio-5172 were composed of paraffin only, with the ratio of n-/iso- being 0.06 and 0.80, respectively. The lower the degree of branching is in paraffin, the faster the isomerization of peroxy radical is produced during oxidation, which could determine the propagation rate of the ignition. Therefore, Bio-5172, composed of more n-paraffin, possesses shorter ignition delay time compared with Bio-7629.

• Journal of Photoscience
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• v.3 no.2
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• pp.91-93
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• 1996

In connection with our interest on the photochemical properties of heteroaryl halides, which are currently the subject of heterocyclic ring formation and haloarene degradation, we have studied the photochemistry of the haloarene linked to N-heteroarene compounds. Imidazo[5,1-a]isoindole was synthesized from N-(ochlorobenzyl)imidazole or N-(o-bromobenzyl) imidazole in acidic aqueous solution or acetonitrile via the intramolgcular photocyclization (Table 1). This type of reaction provides the synthetic methods for 5- and 6-membered polyheteroatomic heterocyclic ring compounds. However, the reaction mechanism for the intramolecular photocyclization of haloarene tethered heteroarenes has not yet been established. Grimshaw et al. suggested a mechanism for homolyric carbonhalogen bond fission assisted by radical complexation to explain their results in the photocyclization of 5-(2-chlorophenyl)-1,3-diphenylpyrazole. They also reported the detection of acyclohexadienyl intermediate involved in the above reaction. Park et al. reported several transient 'intermediates involved in the laser flash photolysis of N-(o-halobenzyl) pyridinium and N-benzyl-2-halopyridinium salts. Thus we performed the laser flash photolysis study on the photocyclization reaction of N-(o-chlorobenzyl) imidazole to identify the intermediate species involved in the reaction. Here, we report on the preliminary results in the photocyclization reaction of N-(o-halobenzyl)imidazole through the detection of reaction intermediates.