• Archives of Pharmacal Research
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• 제21권1호
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• pp.73-75
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• 1998

In summary, six 4-substituted-1-azzanthraquinones were designed and synthesized using hetero Diels-Alder reaction as a key step. Although a great number of reaction conditions for benzylic bromination were examined, this step need to be improved for the efficient synthesis of the related analogues. 4-Bromomethyl-1-azzanthraquinone 6 may have potential for the treatment of tumors resistant to the doxorubicin. The compounds 9 and 10 containing the latent alkylating functionality may need further in depth biological evaluation. Work is in progress to design, synthesize, and evaluate additional compounds in this and related systems.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2712-2714
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• 2010

• Bulletin of the Korean Chemical Society
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• 제23권4호
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• pp.537-538
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• 2002

• Bulletin of the Korean Chemical Society
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• 제12권2호
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• pp.125-126
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• 1991

• Bulletin of the Korean Chemical Society
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• 제17권9호
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• pp.849-853
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• 1996

Hetero Dieis-Alder reactions containing phosphorus atom at various positions of diene and dienophile as well as standard Dieis-Alder reaction between ethylene and cis-l,3-butadiene have been studied using ab initio method. Activation energy showed a good linear relationship with the FMO energy gap between diene and dienophile, which can be normally used to explain Dieis-Alder reactivity. Since π-bond cleavage and σ-bonds formation occur concertedly at the TS, geometrical distortion of diene and dienophile from the reactant to the transition state is the source of barrier. Based on the linear correlations between activation barrier and deformation energy, and between deformation energy and π-bond order change, it was concluded that the activation barrier arises mainly from the breakage of π-bonds in diene and dienophile. Stabilization due to favorable orbital interaction is relatively small. The geometrical distortions raise MO levels of the TS, which is the origin of the activation energy. The lower barrier for the reactions of phosphorus containing dienophile (reactions C, D, and E) can be explained by the electronegativity effect of the phosphorus atom.

• 대한화학회지
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• 제38권9호
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• pp.676-681
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• 1994

4-Acetoxyazetidine-2-one과 (3R,4R)-4-acetoxy-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]azetidin-2-one에 2-(tert-butyldimethylsilyloxy)-1,3-butadiene 또는 3-(tert-butyldimethylsilyloxy)-1,3-pentadiene을 염화아연의 존재하에 반응시켰을 때 Diels-Alder 첨가생성물인 cephem 유도체가 얻어졌다. 이 반응에서 diene으로 tert-butyldiemethylsilyl acrylate를 사용하였을 때에는 azetidin-2-one의 4-위치의 acetoxy기가 acryloyloxy로 치환된 화합물이 얻어졌다. 4-phenylsulfonylazetidin-2-one을 dienophile로 사용하여 2-(tert-butyldimethylsilyloxy)-1,3-butadiene과 반응시켰을 때에는 carbacephem은 생성되지 않았고 4-phenylsulfoyl-2-butanone이 얻어졌다. Thiochalcone dimer를 염화아연의 존재하에 4-acetoxyazetidin-2-one과 반응시켰을 때 azetidin-2-one의 고리가 깨어진 화합물이 생성되었고, N-methylacrylamide를 trimethylsilyl trifluoromethanesulfonate와 triethylamine의 존재하에 반응시켜 얻은 2-trimethylsilyloxy-1-aza-1,3-butadiene은 4-acetoxyazetidin-2-one과 Diels-Alder 유형의 반응을 하지 않았다.

• Korean Chemical Engineering Research
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• 제61권1호
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• pp.168-174
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• 2023

일반적인 메틸 메타아크릴레이트(methyl methacrylate) 상업 공정의 중간체인 메타아크릴 알데히드(methacryl aldehyde)에는 불순물이 존재한다. 이는 전체 화학 반응의 전환율과 선택도가 크게 저하되는 원인이며 메타아릴 알코올(methallyl alcohol) 생산성 향상의 주요 문제이다. 본 연구는 다양한 불순물 중에서 반응성 저하의 주요 원인이 산(acid)임을 발견하였다. 불순물로 존재하는 산은 촉매의 활성을 급격하게 저하시키며, 부반응인 불균일 딜스-알더 반응(hetero Diels-Alder reaction)이 촉진됨을 확인하였다. 따라서, 메타아크릴 알데히드의 카르보닐기(carbonyl group)를 선택적으로 수소화하는 반응에서 반응 불순물인 산을 제거하기 위해 전처리 방법을 비교 평가하였고, 생산성을 향상시키기 위한 효과적인 방법을 제안하였다. 이를 통해 제안된 조건 하에서 최적의 선택적 수소화 반응 조건을 완성하였다.

• 약학회지
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• 제42권3호
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• pp.257-264
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• 1998

5-Methylthebaine was obtained by treating thebaine with n-butyllithium and methylfluorosulfonate. Hetero Diels-Alder reaction of thebaine and 5-methylthebaine with trifluoroacet aldehyde afforded 14-${\beta}$-(triflu-oro-2-hydroxyethyl)codeine (2) and 14-${\beta}$-(trifluoro-2-hydroxyethyl)-5-methylcodeinone (9). 6-${\alpha}$-OH compound (4) was obtained by employing $CeCl_2$ and $NaBH_4$. After synthesized a derivative substituted for 3-OH (5), using boron tribromied, We synthesized a new derivative that make double bond in C-7, C-8 into epoxode (6), (10). Through inspecting an influence on structure-activity and analgetic action, we are going to examine which opiold acceptor has a selectivity.

• 약학회지
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• 제42권5호
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• pp.507-512
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• 1998

In the course of developing novel antitumor intercalating agents. We synthesized 4-carbamoyloxymethyl-l-azaanthraquinones 7-12, incorporating the latent alkylating functi onality. These compounds were designed to explore the effect of substituent on the nitrogen of carbamate. The target compounds were prepared by hetero Diels-Alder reaction as a key step followed by functionalization of benzylic methyl to the desired substituents. Growth inhibitory studies of the azaanthraquinones were conducted in vitro against human cancer cell lines (SNU-354; liver and MCF7; breast) and human epidermoid carcinoma cells that are sensitive (KB-3-1) and multidrug-resistant (KB-V-1). The compounds were less potent than doxorubicin against sensitive cell lines. However, the most active compound 12 was not cross-resistant with doxorubicin against KB-V-1.

• 약학회지
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• 제41권6호
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• pp.718-723
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• 1997

In the course of developing novel antitumor intercalating agents, we synthesized 3- carbamoyloxymethyl-azaanthraquinones 6-12, incorporating the latent alkylating functionality. These compounds were designed to explore the effect of heteroatom incorporation into anthraquinone chromophore and the effect of the incorporation of the latent alkylating functionality. The derivatives were prepared by hetero Diels-Alder reaction as a key step followed by functionality of allylic methyl to the desired substituents. Growth inhibitory studies of the azaanthraquinones were conducted in vitro against human cancer cell lines (SNU-354: liver and MCF7: breast) and human epidermoid carcinoma cells that are sensitive (KB-3-1) and multidrug-resistant (KB-V-1). The derivatives were 10 to 100-fold less potent than doxorubicin against sensitive cell lines. However, they were marginally cross-resistant with doxorubicin against KB-V-1.