• Proceeding of EDISON Challenge
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• 2013.04a
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• pp.101-109
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• 2013

Diels-Alder 반응은 유기합성에서 중요하게 다뤄지는 고리형성 반응으로 위치 선택성과 더불어 단일 단계 반응이기에 특이한 입체 선택성을 갖는 것으로 알려졌다. 그러나 실제로는 단계적 반응 경로도 존재할 수 있음을 발견하였는데, 이 경우에 갖는 위치 선택성과 입체 선택성은 달라질 가능성이 높다. Density Functional Theorem(DFT)로 계산한 결과, 비대칭 Diels-Alder 에 대해 단계적 반응의 경우에도 마찬가지로 유사 ortho 형태에 endo 지향성을 나타내었지만 대칭 Diels-Alder 반응에 비해 단계적 반응이 일어나기 힘들다는 결론을 얻을 수 있었다.

• The Korean Journal of Ecology
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• v.1 no.2
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• pp.57-65
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• 1977

The biomass and net production of alder and oak trees was estimated by allometric method. The productivity of the two stands of alder and oak was obviously different judging from the rate of photosynthesis productive structure and vertical distribution of light. The amounts of net photosynthesis under the saturated light were 2.31, 1.42mg $CO_2/dm^2\cdot$hr. in the sun and shade leaves of alder tree and 1.58, 0.84mg $CO_2/dm^2\cdot$hr in that of the oak, respectively. Total annual respiration loss calculated from the respiration measured at $25^{\circ}C$ and the mean air temperature from every 10 days were 13.56ton/ha.yr in the alder stand and 19.83 ton/ha.yr in the oak. The productive structure and the vertical distribution of light in the stand were assumedly more effective to produce dry matter in the oak stand than in the alder. The biiomasses measured in 1975 and 1976 were 51.51 and 56.82 ton/ha in the alder stand and 73.35, 86.77 ton/ha in the oak one, respectively. Annual net production and gross production were 8.56 and 22.12 ton/ha.yr in the alder stand but those were 17.90 and 37.74 ton/ha.yr in the oak stand. The ratios of respiration to gross procution (R/Pg) were prespectively 0.61 and 0.53 inthe alder and oak stands. Efficiencies of solar energy utilizaztion of net production during the growing season(May-Oct.) were 0.67 and 1.40% and those of gross production were 1.72 and 2.94% in the alder and oak stands respectively.

• Journal of the Korean Chemical Society
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• v.45 no.3
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• pp.207-212
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• 2001

DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4-DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular Orbital) energies for the optimized 1,4-disubstituted-1,4-DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively.

• Journal of Forest and Environmental Science
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• v.28 no.4
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• pp.232-241
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• 2012

We investigated the relationship between vegetation type and soil carbon dynamics in even-aged alder (Alnus hirsuta) and Korean pine (Pinus koraiensis) plantations in central Korea. Both forests were located on the same soil parent material and occupied similar topographic positions. Soil $CO_2$ efflux in the two plantations was determined using a dynamic chamber method accompanied by measurements of soil moisture content and temperature. Mean soil temperature was similar in the two plantations, but mean soil water content was significantly higher in the alder plantation than in the pine plantation. In both plantations, seasonal patterns in soil $CO_2$ efflux exhibited pronounced variation that corresponded to soil temperature. Soil water content did not affect the seasonal variation in soil $CO_2$ efflux. However, in summer, when soil temperature was above $17^{\circ}C$, soil $CO_2$ efflux increased linearly with soil water content in the alder plantation. Estimated $Q_{10}$ was 3.3 for the alder plantation and 2.7 for the pine plantation. Mean soil respiration during the measurement period in the alder plantation was 0.43 g $CO_2\;m^{-2}\;h^{-1}$, which was 1.3 times higher than in the pine plantation (0.33 g $CO_2\;m^{-2}\;h^{-1}$). Higher soil $CO_2$ efflux in the alder plantation might be related to nitrogen availability, particularly the concentration of $NO_3{^-}$, which was measured using the ion-exchange resin bag method.

• Archives of Pharmacal Research
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• v.9 no.1
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• pp.19-20
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• 1986

Reaction of dine alcohol 5 and maleic anhydride in benzene at either room temperature or reflux proceeds probably through a intermolecular Diels-Alder cycloaddition followed by lactone formation to give adduct 6.

• Bulletin of the Korean Chemical Society
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• v.24 no.1
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• pp.13-14
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• 2003

• Bulletin of the Korean Chemical Society
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• v.29 no.10
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• pp.1898-1904
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• 2008

Study of computational model of the concerted Diels-Alder reaction between 9,10-dimethyl anthracene (as donor) and tetracyanoethylene (as acceptor) in absence and in presence of aromatic solvents (benzene, mesitylene and hexamethylbenzene, as donors) using an AM1 semi-empirical method. AM1 method used to study the neutral charge transfer complex models that could be expected between donor and acceptor during the course of the concerted Diels-Alder reaction. Calculated enthalpies of reaction of the charge transfer complexes models showed physical and chemical meaning for explain the effect of aromatic solvents on the kinetic process of concerted Diels-Alder reaction that contains tetracyanoethylene.

• Proceeding of EDISON Challenge
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• 2013.04a
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• pp.153-165
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• 2013

카이랄 ${\alpha},{\beta}$-불포화 N-Acyloxazolidinone은 Diels-Alder 반응의 친다이엔체로서 dialkylaluminium chloride 촉매하에서 높은 반응성과 부분입체선택성을 가지는 것이 이미 실험적으로 알려져 왔다. 제안된 Diels-Alder 반응의 메커니즘을 토대로 진행한 DFT 계산에서 dimethylaluminium chloride(이하 DMAC)는 $TiCl_4$에 비해 높은 endo 선택성을 띄는 반면, $TiCl_4$는 부분입체선택성에서 우세했다. 특히 DMAC는 현저히 낮은 활성화 에너지를 나타내어 이론적으로 반응속도의 측면에서 상당한 이득이 있음을 예측할 수 있다. 또한 chiral auxiliary로서 phenyl과 isopropyl은 구조적인 차이로 인해 선택성에서 역시 차이를 보였다. 계산화학적인 방법을 통한 입체선택적 Diels-Alder 반응의 분석은 알려진 메커니즘에 대한 명확한 증거를 제시할 뿐만 아니라 다른 유기합성 반응에 있어서 새로운 반응을 개발하는 데 이론적인 근거를 뒷받침 한다.

• Journal of the Korean Chemical Society
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• v.17 no.1
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• pp.1-9
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• 1973

The purpose of this paper is to investigate the mechanism of Diels-Alder reaction by assuming pseudo molecular complex (PMC) which has characters both of ionic and radical bonds. We treated this complex quantum-chemically as an intermediate between the configuration without charge transfer (radical bond character) and the configuration corresponding to the charge transfer from Diene (R) to Dienophile (S) (ionic bond character). The wave function for the complex could be expressed as: ${\psi}_{complex} = {\psi}(R,S) +{ \rho}{\psi}(R^+,S^-)$ where ${\rho}$ is the extent of charge transfer which is a constant to measure the ionic character of PMC. It has been noticed that${\rho}$is related to the difference between Fr + Fr' and Fs + Fs' in free valence (F) when R is united to S through atom r in R to atom s in S and atom r' in R to atom s' in S, That is, ${\rho}{\alpha}$ ${\Delta}F = (Fr + Fr') - (Fs + Fs')$. We have calculated ${\Delta}F$values for more than forty Diels-Alder reactions. The calculated values of ${\Delta}F$ is reversely proportional to the values of Brown's paralocalization energy (Lp) as well as Dewar's differences of delocalization energy$({\Delta}Edeloc.)$ with good linearity. This approach also presents a way of predicting the possibility and the easiness of diene synthesis between any two conjugate compounds. According to the considerations, it could be concluded that Diels-Alder reaction takes place through the united ionic-radical mechanism rather than the separated ionic or radical mechanism.

• Journal of the Korean Chemical Society
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• v.23 no.5
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• pp.286-295
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• 1979

In order to predict the effect of Lewis acid catalysis on the regioselectivity of the Diels-Alder reactions between unsymmetrically substituted dienes and dienophiles, the frontier orbital theory applied to the theoretical model of the Lewis acid complexed dienophile was studied by means of CNDO/2 MO. In the majority of reactions, CNDO/2 calculations gave good results in accordance with experimental orientation. Also, it was shown that the secondary orbital interaction played an important role in the regioselectivity of the Diels-Alder reaction between unsymmetrically substituted dienes and dienophiles. Although ANH's treatment is mathematically simpler than other methods, ANH's method which laid emphasis on dissymmetrical transition state gave good results on decision of regioselectivity.