• Bulletin of the Korean Chemical Society
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• 제20권12호
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• pp.1433-1436
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• 1999

The 2-(2,4-dimethoxyphenyl)-4-MDO (2) underwent polymerization with ring opening as well as cyclization reaction in the presence of various cationic catalysts such as boron trifluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid and trifluoroacetic acid. They afforded a mixture of the ring-opened poly(keto ether) and 3(2H)-dihydrofuranone derivative. Both the methylene group and oxygen atom of 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The contents of the polymer and cyclization product were variable according to the acid strength of the cationic catalysts.

• Bulletin of the Korean Chemical Society
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• 제15권8호
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• pp.680-684
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• 1994

Pilocarpine analogs were prepared by empoying a radical cyclization reaction as a key step for the five-membered ring formation.

• Bulletin of the Korean Chemical Society
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• 제20권6호
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• pp.663-666
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• 1999

The 4-methylene-1,3-dioxolane(4-MDO) derivatives with dimethoxyphenyl group on the 2-position of 1,3-dioxolane ring, 2-(x,y-dimethoxyphenyl)-4-MDO derivatives (x,y=2,3(1b), 2,4(2b), 2,5(3b) and 3,4(4b)) were prepared by acelalizationof the corresponding benzaldehyde with 3-chloro-1,2-propanediol, followed by dehydrochlorination. 2-(Dimethoxy)phenyl-4-MDO derivatives underwent polymerization wiht ring opening as will as cyclization reaction to afford a mixture of the ring-opened polymer and 3(2H)-dihydrofuranone derivative with boron trifluoride as a cationic catalyst. Both the methylene group and 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The key intermediate of the polymerization is a benzyl cation generated by ring opening, and the cyclization reaction proceed via proton addition to oxygen atom of 1,3-dioxolane ring.

• Bulletin of the Korean Chemical Society
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• 제31권3호
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• pp.557-558
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• 2010

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1195-1199
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• 1999

2-(2,4,5-Trimethoxyphenyl)-4-methylene-1,3-dioxolane (1b), 2-(2,4,6-trimethoxyphenyl)-4-methylene-1,3-di-oxolane (2b), and 2-(3,4,5-trimethoxyphenyl)-4-methylene-1,3-dioxolane (3b) were prepared and polymerized with boron trifluoride. Boron trifluoride catalyzed reaction proceeded via mainly ring-opening polymerization and cyclization reaction to yield poly(keto ether) and 3(2H)-dihydrofuranone. The yields of polymer and cyclized product exhibited a dependency on the position of the methoxy substituents in the benzene ring of 2-phenyl-4-methylene-1,3-dioxolane derivatives. Electrophilic attack of methylene or oxygen atom on 4-meth-ylene-1,3-dioxolane ring were suggested for the polymerization and cyclization.

• Journal of Photoscience
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• 제4권1호
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• pp.7-10
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• 1997

The structures of 8-membered azalactone isomers produced from photocyclization of 2-(N,N-dibenzylamino)ethyl benzoylacetate were determined by the X-ray structure analysis to clarify the stereochemical behavior of a 1,8-biradical. The remarkable stereoselectivity in cyclization of the 1,8-biradical to form cis- and trans-isomers of the azalactone was not observed. The ring conformations were boat-chair like and dihedral angles between C$_5$- and C$_6$- phenyl groups were ca 45$\circ$ in the both isomers. The 1,8-biradicals in the transition state for the cyclization would have nearly same boat-chair like conformation and twisted configuration with the dihedral angle of ca 45$\circ$ as the corresponding isomer, and this is responsible for luck of stereoselectivity in long-chain biradical cyclization.

• Bulletin of the Korean Chemical Society
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• 제22권9호
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• pp.999-1004
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• 2001

(1-Chloro-2,2-dicyanovinyl)benzene or 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene was reacted with 2-amino-phenol to give the model compound, hydroxy enaminonitrile, which was found to undergo thermal cyclization reaction to form the corresponding benzoxazole. This intramolecular cyclization reaction is expected to occur through nucleophilic attack to electropositive enamine carbon by ortho-hydroxy group on the phenyl ring, which is accompanied by the release of neutral malononitrile through rearrangement. From each bifunctional monomer, o-hydroxy substituted polyenaminonitrile was prepared and characterized as a new precursor polymer for well-known aromatic polybenzoxazole. Also the unusual macrocyclic dimer formation from the 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane polymerization reaction system was discussed. The thermal cyclization reactions and the properties of polymers were investigated using FT-IR and thermal analysis (DSC & TGA).

• 약학회지
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• 제39권1호
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• pp.31-35
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• 1995

An unusual 10-membered lactone possesing ring-olefin at 7, 8-position has been efficiently synthesized. The $\omega$-hydroxy acid as a cyclization precusor was derived from $\varepsilon$-caprolactone in 41% overall yield of 7 steps and efficiently cyclized by Mukaiyama procedure.

• Bulletin of the Korean Chemical Society
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• 제25권2호
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• pp.207-212
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• 2004

In this study, we attempted to prepare compounds with heterocyclic replacements for metabolically unstable esters of benzopyranyl indole-2-carboxylic esters, which showed good in vitro and in vivo cardioprotective efficacies possibly through the opening of mitochondrial ATP-sensitive potassium channel ($K_{ATP}$). Initially, we tried to construct indolin-2-yl-heterocycles using unprotected indoline-2-carboxylic acid, but the cyclization was proceeded with oxidation of the indoline ring to the indole, which didn't react with benzopyranyl epoxide. Thus we introduced N-Boc group to deplete the electron density of the indoline ring. We successfully prepared various indolin-2-yl-heterocycles by the cyclization of the building blocks including carboxamide, ${\beta}$-hydroxy amide, hydrazide, nitrile starting from N-Boc-indoline-2-carboxylic acid.

• 분석과학
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• 제8권4호
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• pp.649-654
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• 1995

The reactivity of superoxide ion($O{_2}^{-.}$) with halogenated substrates is investigated by cyclic voltammetry and rotated ring-disk electrode method in aprotic solvents. The more positive the reduction potential of the substituted nitrile, the more facile is nucleophilic displacement by $O{_2}^{-.}$. The reaction rates of halogenonitriles with $O{_2}^{-.}$ vary according to the leaving-group propensity of halide (Br>Cl>F). The relative reaction rates of other substituted nitriles are in the order of electron-withdrawing propensity of the substituent group (CN> $C(O)NH_2$ >Ph, $CH_2CN$). The reaction of $O{_2}^{-.}$ with dihalocarbons indicates that five-membered rings can be rapidly formed by the cyclization of substrate and $O{_2}^{-.}$, and the relative rates of cyclization depend on the number of methylenic carbons {$Br(CH_2)_nBr$, [n=1<2<3>4>5]}. Mechanisms are proposed for the reaction of $O{_2}^{-.}$ with halogenated substrates.