• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1851-1858
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• 2011

Details of the double-bond isomerization of 1-hexene over H-ZSM-5 were clarified using density functional theory. It is found that the reaction proceeds by a mechanism which involves the Br${\o}$nsted acid part of the zeolite solely. According to this mechanism, 1-hexene is first physically adsorbed on the acidic site, and then, the acidic proton transfers to one carbon atom of the double bond, while the other carbon atom of the double bond bonds with the Br${\o}$nsted host oxygen, yielding a stable alkoxy intermediate. Thereafter, the Br${\o}$nsted host oxygen abstracts a hydrogen atom from the $C_6H_{13}$ fragment and the C-O bond is broken, restoring the acidic site and yielding trans-2-hexene. The calculated activation barrier is 12.65 kcal/mol, which is in good agreement with the experimental value. These results well explain the energetic aspects during the course of double-bond isomerization and extend the understanding of the nature of the zeolite active sites.

• Journal of Photoscience
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• 제9권2호
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• pp.1-4
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• 2002

Hula-twist is a volume-conserving photoisomerization reaction mechanism postulated in 1985 to account for the rapid photoisomerization of the retinyl chromophore in rhodopsin. The requisite stereochemical consequence of simultaneous isomerization of a double bond and an adjacent single bond has recently been demonstrated in isomerization of pre-vitamin D in an organic glass and by many other examples of organic systems already reported in the literature This paper reports the consequence in applying the mechanism to the primary photochemical process of several photosensitive biopigments: bilirubin, photoactive yellow protein, bacteriorhodopsin and rhodopsin. It is shown that the anchored nature of the chromophores must first be taken into consideration.

• Journal of Photoscience
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• 제5권2호
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• pp.47-51
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• 1998

Direct irradiation of 1Z,3E-1-cyano-1,4-diphenylbutadiene (2) and 1Z,3E-1-cyano-3-methyl-1,4-diphenylbutadiene (3) in organic solvents viz. n-hexane, methanol and acetonitrile results in preferential isomerization of the double bond substituted with cyano group via one-photon-one-bond isomerization process. The quantum efficiency of the isomerization of 3 is more than 2 in all the three solvents. Photoproducts of 2 and 3 (viz. 2a, 2b, 3a, 3b) also exhibited similar photoisomerization trends. The results are discussed in terms of the effects of substituents on the potential energy surface of the excited singlet states of $\alpha$,$\omega$-diphenylpolyenes, and the role of zwitterionic dipolar species in the photoisomerization process of linearly conjugated C=C polyenes is highlighted.

• Bulletin of the Korean Chemical Society
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• 제29권11호
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• pp.2202-2204
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• 2008

• Bulletin of the Korean Chemical Society
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• 제7권6호
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• pp.468-471
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• 1986

The isolated products from the reactions of $Rh(ClO_4)(CO)(PPh_3)_2$ (1) with CH_2$ = $CHCO_2C_2H_5$ (2) and trans-$CH_3CH$ = $CHCO_2C_2H_5$ (3) contain 80∼ 90% of $[Rh(CH_2 = CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ (4) and [Rh(trans-$CH_3CH = CHCO_2C_2H_5(CO)(PPh_3)_2]ClO_4$ (5), respectively where 2 and 3 seem to be coordinated through the carbonyl oxygen. It has been found that complex 1 catalyzes the isomerization of $CH_2 = CH(CH_2)_8CO_2C_2H_5$ (6) to $CH_3(CH_2)_nCH = CH(CH_2)_{7-n}CO_2C_2H_5$ (n = 0∼7) under nitrogen at 25$^{\circ}C$. The isomerization of 6 is slower than that of $CH_2 = CH(CH_2)_9CH_3$ to $CH_3(CH_2)_nCH$ = $CH(CH_2)_{8-n}CH_3$ (n = 0∼8), which is understood in terms of the interactions between the carbonyl oxygen of 6 and the catalyst. It has been also observed that complex 1 catalyzes the hydrogenation of 2, 3, 6, trans-$C_6H_5CH = CHCO_2C_2H_5$ (7), $CH_3(CH_2)_7CH = CH(CH_2)_7CO_2C_2H_5$ (8) and $CH_2 = CH(CH_2)_9CH_3$ (9), and the isomerization (double bond migration) of 6 and 9 under hydrogen at 25$^{\circ}C$. The interactions between the carbonyl oxygen of the unsaturated esters and the catalyst affect the hydrogenation in such a way that the hydrogenation of the unsaturated esters becomes slower than that of simple olefins.

• 대한약학회:학술대회논문집
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• 대한약학회 2002년도 Proceedings of the Convention of the Pharmaceutical Society of Korea Vol.2
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• pp.231.1-231.1
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• 2002

The anaerobic pathway for unsaturated fatty acid biosynthesis was established in the 1960s in Escherichia coli. The double bond is introduced into the growing acyl chain by FabA., an enzyme capable of both the dehydration of ${\beta}$-hydroxdecanoyl-［acyl carrier protein］ (ACP) to trans-2-decenoyl-ACP. and the isomerization of trans-2 to cis-3-decenoyl-ACP. However. there are a number of anaerobic bacteria whose genomes do not contain a fabA homolog, but these organisms nonetheless produce unsaturated fatty acids. (omitted)

• 한국식품영양학회지
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• 제11권1호
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• pp.26-30
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• 1998

옥수수 기름의 탈취온도가 trans 지방산 생성량 및 그 조성에 미치는 영향을 GLC를 이용하여 측정하였다. 상대적으로 저온탈취인 240~25$0^{\circ}C$에서는 극미량의 trans 지방산만이 검출되었으나, 고온탈취인 255~27$0^{\circ}C$ 구간에서는 0.30, 0.57, 0.64 및 0.81%를 나타내었다. 이성화 현상은 이중결합수가 증가할수록 두드러졌으며, tt 및 ttt형은 거의 검출되지 않았는데 비하여 ct, cct 및 tcc형이 다량 검출되었다. 따라서, 탈취유의 이화학적 특성과 함께 이성체형성의 극소화는 저온탈취에 의하여 최대의 효과를 얻을 수 있음을 확인하였다.

• Archives of Pharmacal Research
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• 제29권10호
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• pp.840-844
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• 2006

For the exploration of pharmacophoric moiety of malloapelta B (1) possessing the inhibitory activity of $NF-{\kappa}B$ activation, structural variation of ${\alpha},{\beta}-unsaturated$ carbonyl motif was attempted. 1 was reduced by catalytic hydrogenation, sodium borohydride, and lithium aluminumhydride. Catalytic hydrogenation with 30 psi or 15 psi of $H_2$ gas of 1 generated 8-butyl-5,7-dimethoxy-2,2-dimethylchroman (2) and 1-(5,7-dimethoxy-2,2-dimethylchroman-8-yl)butan-1-one (3), respectively. Reduction with sodium borohydride occurred at the double bond of ${\alpha},{\beta}-unsaturated$ ketone of 1 to give 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)butan-1-one (4). Reduction of 1 with lithium aluminumhydride and then quenched with methanol and water produced unexpected products, 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)-3-methoxy-1-butene (5) and 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)-3-hydroxy-1-butene (6). These are formed from the isomerization of initial product 9 through the continuous conjugate carbocation intermediate 11. Addition of ethylmagnesium bromide and dimethyl malonate anion to 1 gave the conjugate adducts 7 and 8. Ethylmagesium bromide and sodium borohydride reduction unusually gave the conjugate addition due to steric congestion around carbonyl group of 1. Compound 2 exhibits the reduced inhibitory activity against $NF-{\kappa}B$ activation and the others do not show the activity. Therefore ${\alpha},{\beta}-unsaturated$ carbonyl group of 1 should be important for its inhibitory activity.

• Journal of the Korean Wood Science and Technology
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• 제16권2호
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• pp.79-89
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• 1988

본(本) 실험(實驗)은 리기다소나무(Pinus rigida Mill)를 petroleum ether로 추출(抽出)한 추출액(抽出被)과 흑액(黑液)으로부터 얻은 tall oil과의 조성(組成)의 변화(變化)를 조사(調査)하기 위하여 실시(實施)하였다. 생재(生材)의 유기용매(有機溶媒) 추출액(抽出液)과 tall oil 을 DEAE-Sephadex 칼럼과 aluminum oxide 칼럼을 사용하여 수지산(樹脂酸)과 지방산(脂肪酸)으로 분리(分離)한 후 이를 개스크로마토 그래프로 분석(分析)하였다. 본(本) 실험(實驗)에서 얻는 결과(結果)는 다음과 같다. 생재(生材)의 유기용매(有機溶媒) 추출액(抽出液힘)과 tail oil은 주로 수지산(樹脂酸)으로 구성(構成)되어 있고 특히 abietic-type acide의 함량(含量)이 매우 높게 나타났으며, tall oil의 조성(組成)은 생재(生材)의 유기용매(有機溶媒) 추출물(抽出物)에 비(比)해 지방산(脂肪酸)의 함량(含量)이 증가(增加)한 반면 수지산(樹脂酸)은 감소(減少)하였고, 증해시(蒸解時) 고온(高溫)과 증해약품(蒸解藥品)에 의하여 불포화(不飽和) 지방산(脂肪酸)의 이중결합(二重結合) 위치(位置)의 변화(變化) 및 이성질화(異性質化)에 의하여 미확인(未確認) 물질(物質)의 양(量)이 증가(增加)하였다.