• Bulletin of the Korean Chemical Society
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• 제34권12호
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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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• 제31권9호
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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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• 제28권11호
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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.

• 대한화학회지
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• 제55권5호
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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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• 제25권10호
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• pp.1459-1460
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• 2004

• Bulletin of the Korean Chemical Society
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• 제31권10호
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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.

• 한국추진공학회:학술대회논문집
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• 한국추진공학회 2010년도 제35회 추계학술대회논문집
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• pp.294-299
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• 2010

본 연구의 목적은 열안정성을 향상시키는 첨가제 (열안정제)를 이용하여 exo-tetrahydrodicyclopentadiene (exo-THDCP, $C_{10}H_{16}$)의 열안정성을 향상시키는 것이다. 실험은 반응 진행 중 미량의 시료 추출이 가능한 회분식 반응기에서 수행되었다. 추출한 시료를 gas chromatography-mass spectrometry (GC-MS)를 이용해 성분 분석하여 첨가제 성능-exo-THDCP의 열분해성-을 확인하고, 반응시간에 따른 exo-THDCP의 분해생성물의 성분 및 조성 변화를 통해 첨가제의 작용 메커니즘을 규명하였다. 열안정제로써 수소공여체를 사용하여 실험한 결과 1,2,3,4-tetrahydroquinoline (THQ), benzyl alcohol (BnOH) 등을 첨가하였을 때 exo-THDCP의 열안정성이 향상되었다. 이러한 수소공여체 물질들은 개시반응이 진행된 exo-THDCP 라디칼에 수소원자 (hydrogen radical)를 제공함으로 라디칼의 반응성을 완화시켜 1차 생성물의 활성을 감소시키어 2차생성물질인 $C_{11}$ 이상 생성물의 발생을 감소시키는 것으로 밝혀졌다.

• 청정기술
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• 제26권3호
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• pp.204-210
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• 2020

본 연구에서는 F-T 공정을 통해 합성하여 제조한 바이오항공유(Bio-7629, Bio-5172)와 기존에 사용 중인 석유계항공유(Jet A-1)의 점화특성을 비교하여 분석하였다. Combustion research unit (CRU) 장비를 활용하여 각 항공유의 점화지연시간을 측정하였고, 그 결과를 연료의 물성 및 구성 화합물에 대한 분석을 통해 해석하고자 하였다. 점화지연시간은 Bio-5172가 가장 짧게 측정되었으며 Jet A-1이 가장 길게 측정되었다. 이는 물리적 점화지연시간에 영향을 줄 수 있는 연료의 물성 측면에서 Jet A-1이 가장 큰 표면장력을 가지며 Bio-5172가 가장 낮은 점도를 갖기 때문인 것으로 해석된다. 또한, 각 연료를 구성하는 화합물의 종류 및 비율에 대하여 분석한 결과, 실험 대상 바이오항공유에 없는 방향족화합물이 Jet A-1에는 약 22.8%의 비율로 존재함을 확인하였다. 이는 산화 과정 시에 비교적 반응성이 낮은 benzyl radical을 생성하여 점화지연시간이 길게 측정되는 데에 영향을 주는 것으로 판단된다. Bio-7629와 Bio-5172는 paraffin으로만 구성되어 있으며, n-/iso-의 값은 각각 0.06, 0.80으로 큰 차이를 보였다. 가지화 된 정도가 낮은 paraffin일수록 산화 시에 생성되는 peroxy radical의 이성질화가 빠르게 진행되어 점화의 전파속도 또한 빨라진다. 따라서 n-paraffin의 함량이 비교적 높은 Bio-5172의 경우에 점화지연시간 또한 짧게 측정된 것으로 해석된다.

• Journal of Photoscience
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• 제3권2호
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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.