• 한국식품영양학회지
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• 제7권1호
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• pp.29-35
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• 1994

Photolysis of diazotetracyanocyclopentadiene has been investigated by means of IR and UV-vis spec troscopy in Ar matrix. Parent carbene is produced in low yield and could be detected by UV-vis spectroscopy and IR spectroscopy. The carbene produced from the diazo compound is very photolabile and also decay thermally at temperature as low as 10K. When the diazo compound is photolyzed the Arrhenius plots show a tunneling effect that is not shown as non linearity.

• Journal of Photoscience
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• 제7권1호
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• pp.15-19
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• 2000

The photochemical reaction mechanism has been investigated for methanol insertion into the p-substituted phenylketo carbenes. The triplet spin state of phenyl koto carbene is stabilized by the neighbored carbonyl electrons. When the phenylketo carbene reacts with methanol, the ylied intermediate is formed, then moves to the activated transition state.

• 한국식품영양학회지
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• 제11권3호
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• pp.267-271
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• 1998

Seyferth 시약인 phenyl(tribromomethyl) mercury 및 diazomethane의 식품보존제인 dehydroacetic acid 및 coumarin과의 발암성과 그 반응기작을 분자 구조적 관점에서 알아보기 위하여 UV/vis 조건과 laser flash photolysis 시켰을 때의 결과는 다음과 같다. 1. Diazomethane과 Phenyl(tribromomethyl) mercury와 dehydroacetic acid와 diazomethane과의 반응은 광화학적 분해 반응에서 생성된 : CBr2와 : CH2 카르벤 중간체의 이탈기 효과에 따라 발암성이 크게 나타났다. 2. laser flash photolysis 상에서 반응시켰을 때 식품보존제의 발암성이 UV/vis 상에서의 photolysis 때보다 크게 나타났다.

• Bulletin of the Korean Chemical Society
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• 제10권4호
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• pp.374-377
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• 1989

Photolysis of dichlorodiphenylmethane in glassy 2-MeTHF at 77K results in the formation of diphenylcarbene and the diphenylchloromethyl radical, which were detected by their flourescence emission and excitation spectra. The relative yield of the carbene to radical is shown to vary dramatically as a function of irradiation time. The photolability of the radical is also demonstated. These results were interpreted in terms of a two step mechanism, where the diphenylchloromethyl radical is an intermediate in the formation of diphenylcarbene.

• Bulletin of the Korean Chemical Society
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• 제26권12호
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• pp.1981-1985
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• 2005

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

• 한국식품영양학회지
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• 제10권1호
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• pp.6-13
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• 1997

여러 종류의 coumarin 유도체가 광화학 반응에 의하여 OH·라디칼을 생성하는 반응을 ESR 및 레이저 섬광분해 반응으로 진행시키고 반응속도 상수를 구하여 반응성가 메카니즘을 알아보았다. 본 연구에서 사용된 9종류의 coumarin 유도체는 모두 OH·라디칼 생성반응 메카니즘으로 반응이 진행되었으나 1-ethy1-3-nitro-1-nitrosoguanidine은 광조사에 의해 OH·라디칼 생성반응이 일어나기 전에 분해하여 카르벤 중간체로 변하였다. 9개의 coumarin 유도체는 DMPO-OH 스핀부가 생성물에 해당하는 시그날을 나타내었다. OH·라디칼을 소진시키는 NaN3, EtOH, HCOONa 등은 강한 광증감제로 작용하였다. 수화된 전자의 소멸 THRE 상수는 N20을 첨가했을 때가 K3Fe(CN)6을 첨가했을 때보다 크게 나타났다.