• Bulletin of the Korean Chemical Society
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• 제7권1호
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• pp.25-29
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• 1986

The reaction of cysteine with cinnamaldehyde have been studied kinetically and thermodynamically. It was found that the reaction proceeds in two steps; formation of the monoadduct by a Michael type addition followed by the nucleophilic attack of the second cysteine to the carbonyl carbon of the monoadduct to afford the thiazolidine derivative. A reaction profile for the reaction of cysteine with cinnamaldehyde was constructed based on the thermodynamic parameters analyzed for the forward and the reverse reactions. It was assumed that the second step of this reaction accompanies an intermediate, a Schiff base.

• Bulletin of the Korean Chemical Society
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• 제4권2호
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• pp.95-99
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• 1983

Photoreaction of 8-methoxypsoralen (8-MOP) with thymine (${\ge}$ 300 nm) was carried out in the dioxane-water frozen state. One major and two minor monoaddition products between 8-MOP and thymine were isolated by various chromatographic methods. Major monoadduct was characterized to be a C4 cycloaddition product formed between 5,6-double bond of thymine and 3,4-double bond of 8-MOP with cis-anti stereochemistry. Two minor adducts were proved to be stereoisomers of this major adduct.

• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.554-559
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• 1991

The photophysical and photochemical properties of khellin were compared with those of 8-methoxypsoralen (8-MOP). Quantum yields of fluorescence and triplet formation decreases as solvent polarity increases, which is opposite to 8-MOP, and photocycloadditivity of khellin to olefins is much lower than that of 8-MOP. Electron ejection from khellin by laser flash was not observed, but observed from 8-MOP. As models of 4',5'-monoadducts of khellin or 8-MOP with thymine base, khellin<>dimethylfumarate 4',5'-monoadduct (KDF) was also compared with 8-MOP<>thymidine 4',5'-monoadduct (F-2) in those properties to give some insight on the second-step biadduct formation resulting in cross-links of DNA duplex. KDF and F-2 were very similar to khellin and 8-MOP in photophysical properties, respectively. However, KDF did not form adducts with various olefins, and thus it is thought that 2,3-double bond of chromone moiety in khellin is hardly reactive in contrast with 3,4-double bond of coumarin moiety in 8-MOP. These results indicate that khellin is fairly photostable compound, a poor type Ⅰ photodynamic sensitizer and producer of ${O_2}^{-}$ which is some cause of phototoxic erythemal reactions and undesirable side effects. Therefore khellin is safer to use than 8-MOP in photochemotherapy of some skin diseases. Although khellin is much less reactive than 8-MOP, khellin must be also a monofunctional drug. Since khellin is, however, as effective as 8-MOP in photochemotherapy of some skin diseases, it is suggested that khellin may be different from 8-MOP in the action mechanism.

• Bulletin of the Korean Chemical Society
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• 제25권6호
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• pp.779-785
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• 2004

Syn (or anti) cinnamaldehydeoxime (1a, b) undergoes Diels-Alder addition to tetrabromo-p-benzoquinone (2)in dry xylene in 1 : 1 and 2 : 1 molar ratios to give the mono- and diadducts 3 and 4a, b respectively. The reaction of 3 with thioamides in ethanol gave thiazoloquinoline diones 6a-d, whereas with acid amides in ethylene glycol, it gave oxazoloquinolinediones 12a-f.

• Bulletin of the Korean Chemical Society
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• 제5권6호
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• pp.219-223
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• 1984

The 8-methoxypsoralen$<^{4',5'}_{5',6}>$ thymidine monoadducts are isolated from the irradiation mixture of 8-methoxypsoralen and thymidine in a dry film state by a flash column followed by lobar column chromatography. Some physical properties of the adducts were determined. The fluorescence maximum and quantum yield of the monoadduct are dependent on the solvent polarity and the phosphorescence to fluorescence quantum yield ratio was 2.10 which was significantly increased by external heavy atoms. The phosphorescence lifetime was 1.2s which is relatively large compared to other coumarin derivatives. Accurate spectral data of the monoadducts are presented.

• Bulletin of the Korean Chemical Society
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• 제7권4호
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• pp.289-293
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• 1986

The photocycloaddition reactivity of 5,7-dimethoxycoumarin (DMC) to thymidine is much higher than that of cis-syn 8-methoxypsoralen $<\array{4^{\prime},5\\5^{\prime},6}>$ thymidine monoadducts, due to the steric effect. The different rate is also due to the relative reactivity of the singlet rather than the triplet excited state of the compounds. The biadducts of 8-methoxypsoralen and thymidine are first splitted into 4',5'-monoadducts and thymidine, not into 3,4'-monoadducts and thymidine by 254 nm light.

• 대한화학회지
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• 제26권3호
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• pp.172-178
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• 1982

4',5'-디히드로소랄렌(DHP)을 합성하여 상온 및 77K에서 이 화합물의 형광 양자수율은 0.08, 인광양자수율은 0.013, 형광수명은 0.95ns, 인광수명은 0.039s 임을 알았다. 이 결과로부터 형광수명은 5,7-디메톡시쿠마린보다 작은반면 소랄렌보다 크고 반면 인광수명은 DMC 보다 크고 소랄렌보다 작음을 알았다. 소랄렌 유도체들의 광독성을 분자적 차원에서 규명하고 DNA에의 광부가 반응을 알아내기 위하여 DHP와 TME의 광부가 반응을 연구하였다. 주 생성물은 TLC로 분석하고 Preparative TLC와 용매추출로 분리해냈다. 분리된 생성물의 구조는 질량분석기, UV, IR, NMR 그리고 원소분석결과에 의해 DHP와 TME외 광고리화첨가반응에 의한 생성물 임을 알았다. DHP는 형광의 자체소광 효과를 볼 수 없으며 TME, 에틸푸마레이트, 푸마로니트릴에 의해 형광이 효과적으로 소광된다. 광부가 반응의 양자수율과 소광실험에서 DHP의 광첨가반응은 단일상태와 삼중상태에서 다 일어나는 것으로 추측된다.