• Journal of the Korean Magnetic Resonance Society
• /
• v.22 no.4
• /
• pp.115-118
• /
• 2018

Dipyrromethane 2 functionalized with 3-chloropropyl group on the meso carbon undergoes an unusual intramolecular electrophilic aromatic substitution reaction in the presence of $NaN_3$ instead of a simple nucleophilic substitution reaction. As a result, a new chiral dipyrromethane 1 was synthesized. In this reaction, the ${\beta}$-carbon of the pyrrole ring functions as a nucleophile while the carbon next to the chlorine atom acts as an electrophile. Interestingly, this reaction progresses even in the absence of an acid catalyst. Compound 1 was fully characterized by $^1H-^1H$ and $^1H-^{13}C$ COSY NMR spectroscopic analyses and the high resolution EI mass spectrometry.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.3
• /
• pp.345-354
• /
• 2006

Ionic liquids are alternative reaction media of increasing interest and are regarded as an eco-friendly alternatives, of potential use in place of the volatile organic solvents typically used in current chemical processing methods. They are emerging as the smart and excellent solvents, which are made of positive and negative ions that they are liquids near room temperature. The nucleophilic substitution reaction is one of the important method for inserting functional groups into a carbon skeleton. Many nucleophilic substitution reactions have been found with enhanced reactivity and selectivity in ionic liquid. In this review, some recent interesting results of nucleophilic substitution reactions such as hydroxylations, ether cleavages, carbon-X (X= carbon, oxygen, nitrogen, fluorine) bond forming reactions, and ring opening of epoxides in ionic liquids are discussed.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.12
• /
• pp.1288-1291
• /
• 1997

4-Allylanisole was polymerized with AlCl3 as a catalyst. The polymerization was carried out in nitroethane at various temperatures with changing the ratio of the initiator to the monomer concentration. The weight averge molecular weights measured by gel permeation chromatography in chloroform with polystyrene standards were between 1,500 and 4,700. 1H NMR spectroscopy showed that the polymerization proceeded through a stepwise aromatic electrophilic substitution reaction along with a minor chain-reaction, resulting in a branched polymer. 4-Chloromethylanisole was also polymerized with AlCl3 in nitroethane through an aromatic electrophilic substitution reaction to give a high molecular weight polymer (Mw=88,000).

• Journal of Korea Technical Association of The Pulp and Paper Industry
• /
• v.35 no.1
• /
• pp.41-47
• /
• 2003

Recently, interest in utilization plan of recycling paper have been enhanced. Therefore, this research aimed to develop the manufacture process of cellulose acetate using old newsprint by acetosolv pulping process. And the manufactured cellulose acetate was also analyzed, especially based on chemical properties. The summarized results in this research were as follows; Reaction time, kind and amount of catalyst, and ratio of liquor to material were varied during acetosolv pulping process of old newsprint. Ratio of liquor to material did not give the significant difference in reaction product. Delignification rate was increased with increasing reaction time during acetosolv pulping, but yield and degree of substitution decreased with increasing reaction time. Sulfuric acid are better catalyst than hydrochloric acid in acetosolv pulping process for old newsprint, and optimal addition amount of catalyst was 1% based on reaction material. Delignification, yield, and degree of substitution were influenced by the catalyst and reaction time. Under pulping condition of $120^{\circ}C$ in 1/12 liquor to material ratio and 60min, degree of substitution was about 0.7. The acetylation reaction was not completely caused by these reaction condition. The examination of the FT-IR spectra revealed that absorption band(1200$\textrm{cm}^{-2}$, 1,750$\textrm{cm}^{-1}$) caused by carbonyl group were confirmed.

• Proceedings of the Polymer Society of Korea Conference
• /
• 2006.10a
• /
• pp.195-195
• /
• 2006

A superior electrophilic substitution reaction medium that is non-toxic, relatively less corrosive, and non-volatile electrophilic substitution reaction to afford high molecular weight linear and hyperbranched polyetherketones (PEK' s) was developed. The system has very strong driving force to give extra ordinary high molecular weight linear and hyperbranched PEK' s. The reaction medium was further extended to prepare various types of copolymers and covalently grafted polymers onto carbon nanotube (CNT) or carbon nanofiber (CNF). By using characteristic hydrophilic nature of the reaction medium, hyperbranched PEK' s could be synthesized from commercially available $A_3\;+\;B_2$ monomers without network formation via selective solubility of the monomers.

• Bulletin of the Korean Chemical Society
• /
• v.11 no.1
• /
• pp.65-69
• /
• 1990

The nucleophilic substitution reactions of naphthalene-1,5-disulfonyl chloride and 4-fluorosulfonylbenzenesulfonyl chloride with p-substituted anilines and methyl substituted pyridines in methanol-acetonitrile mixtures and hydrolyses of those disulfonyl halides have been studied by means of conductometric and polarographic methods. A large difference in the selective parameter, ${\rho}_N$ between mono-sulfonyl chloride and disulfonyl halide can be taken as an evidence that the second $SO_2Cl$ grolup of naphthalene-1,5-disulfonyl chloride also takes part in the reaction in contrast to sulfonyl fluoride in 4-fluorosulfonylbenzenesulfonyl chloride, which only acts as a substituent in the nucleophilic substitution reaction.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2011.05a
• /
• pp.244.2-244.2
• /
• 2011

We introduce a novel and robust method for the preparation of nanocomposite multilayers, which allows the excellent photoluminescent (PL) properties as well as the accurate control over the composition and dimensions of multilayers. By exchanging the oleic acid stabilizers of CdSe@ZnS quantum dots (QDs) synthesized in organic solvent with 2-bromo-2-methylpropionic acid (BMPA) in the same solvent, these nanoparticles were be alternately deposited by nucleophilic substitution reaction with highly branched poly(amidoamine) dendrimer (PAMA) through layer-by-layer (LbL) assembly process. Our approach does not need to be transformed into the water-dispersible nanoparticles with electrostatic or hydrogen-bonding groups, which can deteriorate their inherent properties, for the built-up of multilayers. The nanocomposite multilayers including QDs exhibited the strong PL properties achieving densely packed surface coverage as well as long-term PL stability under atmospheric conditions in comparison with those of conventional LbL multilayers based on electrostatic interaction. Furthermore, we demonstrate that the flexible multilayer films with optical properties can be easily prepared using nucleophilic substitution reaction between bromo and amino groups in organic media. This robust and tailored method opens a new route for the design of functional film devices based on nanocomposite multilayers.

• Journal of Photoscience
• /
• v.2 no.2
• /
• pp.77-81
• /
• 1995

Photoreactions of pseudosaccharin ethers have been investigated. Pseudosaccharin 3-allyl ether undergoes a facile photoreaction via reaction pathways involving homolysis of bond between pseudosaccharyl oxygen and 3-allyl carbon, and excited nucleophilic substitution of allyloxy group by solvent which are not quenched by oxygen present in the reaction. Product yield demonstrates that the homolysis pathway predominates over the nucleophilic substitution in ca. 7:1 ratio. In contrast, pseudosaccharin alkyl ethers follow different reaction routes to produce two products, solvent-substituted pseudosaccharin alkyl ethers and reduction products, 3-alkoxy-1, 2-benzisothiazoles. The formations of reduction products, 3-alkoxy-1, 2-benzisothiazoles are completely quenched by oxygen.

• Bulletin of the Korean Chemical Society
• /
• v.21 no.11
• /
• pp.1111-1114
• /
• 2000

The kinetic study of the enaryloxynitriles via the nucleophilic vinylic substitution reaction of various phenol derivatives with 1-chloro-1-phenyl-2,2-dicyanoethene (1) was conducted in the presence of 1,4-diazabicyclo[2,2,2]octane (DABCO). Nucleo philic vinylic substitution of phenol derivatives with electrophilic olefins carrying sluggish leaving group involves a third-order reaction. The reaction was applied to solution polymerization of diphenol derivatives with p-bis(1-chrolo-2,2-dicyanovinyl)benzene (2), which yielded various polyenaryloxynitriles with moderate molecular weight.

• Bulletin of the Korean Chemical Society
• /
• v.12 no.3
• /
• pp.295-301
• /
• 1991

The nucleophilic substitution reactions of p-substituted benzenesulfonyl chlorides wiht p-substituted anilines were carried out in 1,1,1,3,3,3-hexafluoro-2-propanol and 2-propanol mixtures. The salt effect was observed to be inhibited by the reaction of 1,1,1,3,3,3-hexafluoro-2-propanol with nucleophiles. To investigate the effectiveness of the salt for the nucleophilic substitution reaction the relative salt effect was determined. According to the comparison with the inhibitive salt effect and the substituent effects for the substrates and nucleophiles, the reactions were predicted to be controlled by the salt effect more than substituent effect in HFP-PrOH mixtures.