• 폴리머
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• 제38권4호
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• pp.496-501
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• 2014

폴리알파올레핀은 낮은 유동점, 높은 점도지수와 같은 물리화학적 특성이 기존의 광유보다 우수한 합성윤활유이다. 본 논문은 퍼옥사이드계 개시제를 이용하여 올레핀을 사용하지 않고 이소파라핀 분자간의 알킬레이션 반응을 통한 합성 윤활유 제조에 관한 새로운 경로를 제시한다. 평균 탄소수가 i-$C_{16}$, i-$C_{18}$, 그리고 i-$C_{23}$인 세가지 장쇄 이소파라핀의 알킬레이션과 i-$C_{18}$과 2-pentene의 알킬레이션을 di-tert butyl peroxide 라디칼 개시제를 사용하여 여러가지 반응조건에서 수행하여 단독 알킬레이션 반응 경로를 확인하였다. 세가지 유분으로 제조된 알킬레이트를 합성 윤활유로의 적용 가능성을 알아보기 위하여 동점도, 점도지수, 및 유동점을 조사하였다. i-$C_{16}$ 및 i-$C_{18}$ 유분으로 제조된 단독 알킬레이트는 극초고점도지수(>140)와 낮은 유동점(< $-30^{\circ}C$)을 보였다.

• Bulletin of the Korean Chemical Society
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• 제25권1호
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• pp.69-72
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• 2004

The N-alkylation of 4-aminopyrimidine with a tetrahydro-3-aza-cyclopropa[c]inden-5-one, which is a model reaction of the pharmacophore of duocarmycins, was studied with a quantum chemical method. We consider two factors for the acceleration of the N-alkylation; distortion and protonation of the model pharmacophores. The distortion of the spirocyclopropyl moiety in the model spirocyclopropylcyclohexadienone could induce an intrinsic energy of 3-4 kcal/mol, but the protonation on the carbonyl oxygen of the model cyclohexadienone lowers the transition energy of the N-alkylation of 4-aminopyrimidine dramatically (~46 kcal/mol) and is considered to play a major role in the enzyme reaction. The distorted and protonated spirocyclohexadienone is exothermally relieved to a phenol with the heat of reaction of -37 kcal/mol. The protonation process is proposed to be the mode of action of duocarmycins in the DNA alkylation.

• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.559-566
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• 1999

Gas-phase alkylations of delocalized ambident anions, Y---CH---X- where X, Y=CH2, O, or S, have been investigated theoretically at the MP2/6-31+G*//MP2/6-31+G* and QCISD/6-31+G*//MP2/6-31+G* lev-els. O-and S-alkylations (X=O and S) are more favored kinetically by ΔE^≠ = 4.6 and 9.8 kcal mol-1 than the respective C-alkylations even though they are thermodynamically less favored by 22.4 and 6.0 kcal mol-1 respectively. It was found that the transition structures for the C-alkylations are imbalanced due to the endoergic rehybridi-zation of the carbon center from sp2 to sp3 which leads to premature bond contraction of the C-Y bond and delayed bond stretching of the C-X bond. In the O-, or S-alkylation, such endoergic process is not required since the σ-lone pair on O or S is involved in the initial stage of alkylation. The imbalanced TSs for the C-alkylation are accompanied by higher intrinsic barriers and deformation energies.

• 한국응용과학기술학회지
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• 제16권2호
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• pp.117-125
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• 1999

The alkylation benzene with 1-dodecene of Mordenite, Zeolite ${\beta}$ and Zeolite Y was studied in the stirring batch reactor. The kinds of zeolites were found to have influenced the reaction conversion and distribution of phenyldodecane isomer in the product. Compared to the alkylation conducted over Zeolite Y and Zeolite ${\beta}$, the alkylation over Mordenite exhibited higher distribution of 2-phenyldodecane and the alkylation conducted over Zeolite Y and Mordenite, the alkylation over Zeolite ${\beta}$ exhibited higher distribution of heavy alkylate which formed through oligomerization reaction readily deactivated the Lewis acid sites. A special feature of the effect of the benzene to 1-dodecene ratio the reaction conversion and selectivity of phenyldodecane isomer was found. At alkylation of benzene with 1-dodecene over Zeolite ${\beta}$, when the catalyst content in the system was high, the reaction will reach the optimal conversion at the higher B/D. When the benzene to 1-dodecene ratio was high, the selectivity of phenyldodecane isomer is high. It was also found that at the similar reaction conversion there was the same product distribution regardless of D/C ratio.

• 공업화학
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• 제8권2호
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• pp.211-219
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• 1997

1-부텐과 i-부탄의 알킬화반응에 의한 i-옥탄 생성반응을 Cs 혹은 $NH_4$가 치환된 $H_3PW_{12}O_{40}$ 촉매상에서 액상 및 기상으로 수행하였다. 액상알킬화반응의 경우 반응전 촉매의 전처리 온도가 헤테로폴리산 촉매의 반응성에 매우 중요한 역할을 하였다. 액상알킬화반응에서 치환염은 모산보다 매우 우수한 총수율과 i-옥탄 선택도를 보였으며, $(NH_4)_{2.5}H_{0.5}PW_{12}O_{40}$ 촉매는 $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ 보다 1-옥탄 선택도면에서 더욱 효과적인 것으로 나타났다. 기상알킬화반응의 경우 Cs 혹은 $NH_4$가 치환된 $H_3PW_{12}O_{40}$ 촉매의 활성은 촉매의 산특성(산점의 비활성화)과 관련이 있었다. 기상알킬화반응에서 반응초기에는 촉매의 강한 산특성 때문에 $C_5-C_7$가 주로 생성되나 반응이 진행되면서 촉매 산점의 비활성화가 진행되어 $C_8$ 및 $+C_9$가 주로 생성되었다. 기상알킬화반응에서 대상 촉매중 $Cs_{2.5}H_{0.5}PW_{12}O_{40}$이 가장 우수한 총수율을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제26권10호
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• pp.1611-1613
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• 2005

• Archives of Pharmacal Research
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• 제21권4호
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• pp.385-390
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• 1998

Adozelesin and carzelesin are synthetic analogues of the extremely potent antitumor antibiotic CC-1065, which alkylates N3 of adenine in a consensus sequence $5^1$-(A/T)(A/T)$A^*$ ($A^*$ is the site of alkylation). We have investigated the DNA sequence selectivity of adozelesin and carzelesin by thermally ind ced DNA strand cleavage assay using radiolabeled restriction DNA fragments. An analysis of alkylation patterns shows that the consensus sequences for carzelesin and adozelesin have been found to be $5^1$-(A/T)(A/T)$A^*$ and $5^1$-(A/F)(G/C)(A/T)$A^*$. A new consensus sequence, $5^1$-(A/T)(A/T)$CA^*$, has been observed to display an additional alkylation site for adozelesin but not for carzelesin. These results indicate that the pattern of sequence selectivity induced by carzelesin is similar but not identical to those induced by adozelosin.

• Bulletin of the Korean Chemical Society
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• 제23권9호
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• pp.1213-1221
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• 2002

Friedel-Crafts alkylation reaction of an isomeric mixture of 1,2,3,4,5,6,7,8- (2) and 1,2,3,4,5,6,7,8-octahydrophenanthrene (2') with excess vinylchlorosilanes such as vinyl(methyl)dichlorosilane (1a) and vinyltrichlorosilane (1b) in the presence of aluminum chloride catalyst at 80 $^{\circ}C$ gives only one dialkylated products, 9,10-bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydroanthrenes [(Cl2XSiCH2CH2)2C14H16: X = Me (4a), Cl (4b)] in good yields, but 9,10-bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydrophenanthrenes are not obtained. However, monoalkylation of 2 with 1 affords a mixture of both isomeric compounds, 9-[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydroanthracenes 3 and -phenanthrenes 3'. The yield of product 3' is always higher than that of 3. When a mixture of 3 and 3' is alkylated again with 1, only product 4 without phenanthrene type compounds is obtained, indicating that the isomerizations between 2 and 2', or 3 and 3'occur under the alkylation condition. The alkylation with dimethylvinylchlorosilane or trimethylvinylsilane did not proceed. The structure of 4a is determined by X-ray single crystal diffraction analysis.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.847-850
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• 2008

Novel mercaptophenyl carbocyclic C-nucleoside analogue was synthesized via a cyclopentenol intermediate 10, which was prepared using a sequential [3,3]-sigmatropic rearrangement and ring-closing metathesis (RCM). Friedel-Crafts alkylation was then used to couple the thiophenol.

• Archives of Pharmacal Research
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• 제15권4호
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• pp.374-375
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• 1992

The marine sterol (22R, 23R)-methylenecholesterol 1 has been synthesized from readily available C-22 steroidal ester 2 utilizing an intermolecular acyclic ester enolate alkylation as the key step.