• Bulletin of the Korean Chemical Society
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• v.28 no.7
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• pp.1159-1166
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• 2007

New unsymmetrical trans-stilbenes have been prepared by the sequential coupling reactions of bromobenzenesulfonate with formylarylboronic acids, benzylphosphonates and arylmagnesium bromides and characterized. The nickel-catalyzed reactions of stilbenesulfonates with aryl Grignard reagents produced the corresponding stilbenes via the nucleophilic aromatic substitution of the neopentyloxysulfonyl group by aryl nucleophiles. The great chemoselectivity of the alkyloxysulfonyl group allows the stepwise construction of unsymmetrical trans-stilbenes possessing terphenyl moieties. This procedure appears to be a promising and conceptually straightforward route for the parallel synthesis of various unsymmetrical stilbenes as well as other highly conjugated hydrocarbons.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2571-2574
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• 2010

We investigate the mechanism of $S_NAr$ fluorination reactions under the influence of protic solvents and ions. We find that counterion or protic solvent alone retards the $S_NAr$ reactions, but together they may promote the reaction. In this mechanism, the protic solvent acts on the counterion as a Lewis base, and the nucleophile reacts as an ion pair. We also show that an anion (mesylate) may exhibit catalytic effects, suggesting the role of ionic liquids for accelerating the $S_NAr$ reactions.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.895-899
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• 2004

We have designed a new family of radioligands, 3-(amino- and hydroxymethyl)-4-(5-iodopyridin-2-ylthio)indoles, combining characteristically distinct moieties proven to impart successful binding ability in a variety of structurally diverse selective serotonin reuptake inhibitors recently published. Described in this article are the syntheses of 3-substituted 4-(5-iodopyridin-2-ylthio)-indoles, featuring successful adaptation of the modified Leimgruber-Batcho indole synthesis onto the key intermediate 1-(5-iodopyridin-2-ylthio)-2-methyl-3-nitrobenzene (6) prepared from the nucleophilic aromatic substitution of chloropyridine 7 with thiophenol 8.

• Journal of the Korean Chemical Society
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• v.60 no.4
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• pp.251-256
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• 2016

This paper describes the synthesis of alkali metal salts of urea (ureates) and their application to the direct preparation of 4-nitrosoaniline from nitrobenzene via nucleophilic aromatic substitution of hydrogen. Sodium and potassium ureates were readily prepared from the reaction of urea with sodium hydride, metal methoxides, and metal hydroxides. The effect of ureates as nucleophiles on the conversion of nitrobenzene to 4-nitrosoaniline was investigated and compared with that of a urea-metal hydroxide mixture. It was found that the ureates were superior for producing 4-nitrosoaniline owing to their higher thermal stability of the ureate. The ureate obtained from the treatment of urea with sodium hydride gave the highest yield for the preparation of 4-nitrosoaniline. The ureates generated from the reaction of urea with metal hydroxide also gave high yields of 4-nitrosoaniline. Catalytic hydrogenation of 4-nitrosoaniline afforded polymer-grade 1,4-benzenediamine in quantitative yield.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3749-3754
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• 2010

Various terphenyl and quaterphenyl derivatives were prepared by the Ni-NHC catalyzed cross coupling of the corresponding biphenyl- and terphenyl-sulfonates with arylmagnesium bromides. The reactions proceeded rapidly via a nucleophilic aromatic substitution of the alkoxysulfonyl moieties by the aryl nucleophiles to afford high yields within just 1.5 h at room temperature in spite of the low reactivity of the sulfur electrophiles.

• Applied Chemistry for Engineering
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• v.9 no.3
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• pp.440-444
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• 1998

Poly(phenylene sulfide-co-phenylene sulfide sulfone), PPS/PPSS copolymers were synthesized from p-dichlobenzene(DCB), p-dibromobenzene(DBB), p-diiodobenzene(DIB), 4-chlorophenyl sulfone(CPS) and sodium sulfide as comonomers under high temperature and pressure utilizing N-methyl-2-pyrrolidinone(NMP) as solvent. The yield of PPS/PPSS copolymer shoed maximum at $190^{\circ}C$ with [DBB]/[CPS] and [DIB]/[CPS] comonomer pair, while [DCB]/[CPS] pair exhibited maximum yield at $230^{\circ}C$. The change of yield is in the order of I>Br>Cl as leaving groups were in accordance with nucleophilic aromatic substitution reaction mechanism suggested for the synthesis of PPS type polymers. The molecular weight of PPS/PPSS copolymer was the highest($M_w=8,330g/mol$) with [DBB]/[CPS] comonomers in which [CPS] was 10 mole%. The PPS/PPSS copolymer made with 10 mole% of [CPS] showed about $15^{\circ}C$ higher $T_g$ and $15^{\circ}C$ lower $T_m$ than those of PPS homopolymer, which may be useful from the processing and thermal property point of view. The PPS/PPSS copolymer with 30 mole% of CPS or above did not exhibit Tm. The PPS/PPSS copolymer obtained with comonomer feed ratio of [DBB]/[CPS] = 95/5 mole% under $240^{\circ}C$ showed even higher molecular weight($M_w=10,300g/mole$) than PPS homopolymer made under similar reaction condition, retaining high crystallinity and thermal stability.

• Bulletin of the Korean Chemical Society
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• v.24 no.2
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• pp.205-208
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• 2003

Laser-induced Raman spectroscopy has been utilized to demonstrate its feasibility for studying the kinetics of imine formation in chloroform solvent. The imine formation, by the nucleophilic addition of primary amine to the carbonyl group of ketone, has been monitored at ten minute intervals for eight hours. The intensity of the C=O stretching mode at 1684 $cm^{-1}$ was measured to determine the rate constant of the reaction. In order to correct the sample-to-sample fluctuations in Raman peak area, this peak was normalized to the C-Cl bending peak at 666 $cm^{-1}$. By the peak area change during the course of reaction, the second order rates at three different temperatures have been determined. The substituent effects on the π conjugations of imine product have also been investigated. On the basis of Raman frequency shifts, the delocalization properties of the aromatic system modified by substitution of a hydrogen atom with -Cl and $-CH_3O$ groups could be clearly understood.

• Bulletin of the Korean Chemical Society
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• v.24 no.8
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• pp.1181-1187
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• 2003

Condensation of 4-cyano-5,6-dimethyl-3-pyridazinone 1 with aromatic aldehydes gave the novel styryl derivatives 2a-c. Refluxing of compound 2a with phosphorus oxychloride furnished 3-chloropyridazine derivative 3. Compound 3 was reacted with thiourea and produced pyridazine-3(2H)thione 4. Thieno[2,3-c]- pyridazines 5a-e were achieved by cycloalkylation of compound 4 with halocompounds in methanol under reflux and in the presence of sodium methoxide. Also, refluxing of compound 4 with N-substituted chloroacetamide in the presence of potassium carbonate afforded thienopyridazines 6a-e. Cyclization of compound 6 with some electrophilic reagents as carbon disulfide and triethyl orthoformate furnished the novel pyrimido[4',5':4,5]thieno[2,3-c]pyridazines 12 and 13a-c, respectively. Diazotisation of compound 6 with sodium nitrite in acetic acid produced the pyridazino[4',3':4,5]thieno[3,2-d][1,2,3]triazines 14a-c. Ternary condensation of compound 1, aromatic aldehydes and malononitrile in ethanol containing piperidine under reflux afforded the novel phthalazines 16a-c. Compound 3 was subjected to some nucleophilic substitution reactions with amines and sodium azide and formed the aminopyridazines 17a, b and tetrazolo[1,5-b]-pyridazine 19, respectively. The structures of the synthesized compounds were established by elemental and spectral analyses.

• Journal of the Korean Electrochemical Society
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• v.18 no.2
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• pp.75-80
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• 2015

Multi-block sulfonated poly(arylene ether sulfone) (SPAES) copolymer was synthesized via nucleophilic aromatic substitution reaction for proton exchange membrane fuel cell application. After synthesizing the hydrophilic and hydrophobic precursor oligomers having different end-groups (F-terminated or OH-terminated), the effect of end group on the molecular weight was investigated. Hydrophilic oligomers with hydroquinone showed better performance as fuel cell membranes. SPAES membranes showed comparable proton conductivity to that of Nafion at $80^{\circ}C$ and above 70% RH. In particular, SPAES 9 with hydroquinone showed higher proton conductivity than SPAES 10 in the whole RH range studied. Increased local concentration of sulfonic acids within hydrophilic block might develop the hydrophilic-hydrophobic phase separation in the block copolymers.

• Bulletin of the Korean Chemical Society
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• v.28 no.4
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• pp.520-528
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• 2007

A practical and efficient disposal of PCBs (polychlorinated biphenyls) in waste transformer oil by a chemical dechlorination process has been reported. The transformer oil containing commercial PCB mixtures (Aroclor 1242, 1254 and 1260) was treated by the required amounts of PEG 600 (polyethylene glycol 600), potassium hydroxide (KOH) and aluminum (Al), along with different reaction temperatures and times. The reaction of PEG with PCBs under basic condition produces arylpolyglycols, the products of nucleophilic aromatic substitution. The relative efficiencies of PCB treatment process were assessed in terms of destruction and removal efficiency (DRE, %). Under the experimental conditions of PEG600/KOH/Al/100 oC/2hr, average DRE of PCBs was approximately 78%, showing completely removal of PCBs containing 7-9 chlorines on two rings of biphenyl which appear later than PCB no. 183 (2,2',3,4,4',5',6-heptaCB) in retention time of GC/ECD. However, when increasing the reaction temperature and time to 150 oC and 240 min, average DRE of PCBs including the most toxic PCBs (PCB no. 77, 105, 118, 123 and 169) in PCB family reached 99.99% or better, with the exception of PCB no. 5 and 8 (2,3-diCB and 2,4'-diCB). In studying the reaction of PEG with PCBs, it confirmed that the process led to less chlorinated PCBs through a stepwise process with the successive elimination of chlorines. The process also permits complete recovery of treated transformer oil through simple segregating procedures.