• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.240-242
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• 2011

A large scale and commercially feasible synthesis of 5-chloroindole and its 3-substituted analogues has been described via a halogen - halogen exchange reaction from 5-bromoindole and its derivatives using cuprous chloride and dipolar aprotic solvent N-methyl-2-pyrrolidone in one pot with good yields.

• Nuclear Engineering and Technology
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• v.7 no.1
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• pp.25-29
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• 1975

Kinetics of halogen exchange reaction of 1-phenthyl chloride and 2-phenethyl chloride using radioisotopic tracer halide ions in acetone have been studied. The reactions were belived to be S$_{N}$2 processes and the orders of relative nucleophilicity of halide ions were Cl->Br->I-. The reaction rate is slower than that of benzyl chloride. These were interpreted in terms of solvation effect of halide ions and HSAB principle.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.23-28
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• 1965

Halogen exchanges between benzyl chloride and chloride ion have been studied in 90% ethanol-water mixture, and activation parameters in the exchange reaction have been determined; ${\Delta}H^{\neq}$ = 18. 50 Kcal and ${\Delta}S^{\neq}$ = -22. 09 e. u. Results indicated that the reaction proceeded via a typical bimolecular mechanism. The importance of nucleophilic ability of attacking anion in $S_N2$ process has been stressed giving some experimental evidence. The order of reactivity of halides in the exchange reaction is better explained with the Swain's nucleophilic parameter than with the bond dissociation energies.

• Journal of the Korean Chemical Society
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• v.41 no.10
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• pp.552-556
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• 1997

• Journal of the Korean Chemical Society
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• v.13 no.2
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• pp.109-114
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• 1969

Halogen exchange reactions of benzyl halides have been studied in absolute acetone. Rate constants were calculated using an integrated rate expression derived for the reaction involving ion-pair association. The order of nucleophilicity of halide ions in acetone was found to be a reverse of the order in 90% aqueous enthanol solvent. This was interpreted by means of HSAB principle and solvation of halide ions. Net increase in rate of reaction in acetone compared with the rate in protic solvent resulted from large increase in ${\Delta}S^\neq$ rather than decrease in ${\Delta}H^\neq$. The solvation of the transition state also contribute to the net increase in rate.

• Polymer(Korea)
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• v.31 no.6
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• pp.469-473
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• 2007

In this study, oligo(3-methylthiothiophene) was synthesized from thiophene derivative according to the method of reductive coupling using palladium catalyst. For the preparation of monomer, 3-methylthiothiophene was first synthesized through the metal-halogen exchange reaction of 3-bromothiophene with n-butyllithiuim, and the corresponding 2,5-dibromo-3-methylthiothiophene was formed by bromination. Their synthesis and characterization were determined by $^1H-NMR$ and ATR analyses. Thermal stability of the oligothiophene was monitored by thermogravimetric analysis (TGA). Thermal evaporation of the oligo(3-methylthiothiophene) on the substrate was attempted for OTFT applications.

• Journal of the Korean Chemical Society
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• v.42 no.2
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• pp.184-189
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• 1998

Tris(pentafluorophenyl)indium acetonitrile complexes have been prepared from the reaction of Indium trihalides (halogen=Cl, Br) and bis(pentafluorophenyl)cadmium in acetonitrile, and characterized by elementary analysis, $^13C{^1H}-,\; ^1H-\;and\; ^{19}F-NMR$ spectroscopy and mass spectrometry. The Indium (III) compounds were formed stable 1:1 adducts with acetonitrile. $In(C_6F_5)_3{\cdot}DMAP$ has been prepared from the ligand exchange reaction of In$(C_6F_5)_3 {\cdot} CH_3CN$ with DMAP in $CH_2Cl_2 {\cdot} DMAP$ has higher donating character and replaced the $CH_3CN$ through the ligand transfer reaction.

• Journal of the Korean Chemical Society
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• v.19 no.1
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• pp.11-15
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• 1975

Kinetic study of halogen exchange for N,N-dimethylcarbamoyl chloride and N,N-diethylcarbamoyl chloride in acetone by using radioisotopic halide ions has been carried out at two temperatures as a part of studying the reactivity of carbonyl carbon atom. The order of nucleophilicity showed a similar tendency as that for alkyl chloroformate, but reaction rate is much slower than that for solvolysis and alkyl chloroformate. The activation parameters,${\Delta}H^*$and${\Delta}S^*$ were found to decrease in sequence $Cl^{\rightarrow}Br^{\rightarrow}I^-$ for N,N-dialkylcarbamoyl chlorides. The results are interpreted in terms of solvation effect, degree of bond-breaking and bond-formation and electronic requirements.

• Nuclear Engineering and Technology
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• v.5 no.4
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• pp.321-333
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• 1973

The rates and activation parameters for the halide exchange reactions of substituted benzenesulfonylbromides (R-C$_{6}$H$_4$SO$_2$Br, R=p-MeO, p-$CH_3$, p-H, p-NO$_2$) in dry acetone at two temperatures were determined. It was found that the nucleophilicity order of Cl->I-$\geq$Br- for strong electron withdrawing-, and mild electron donating group, and of I-$\geq$Cl->Br- for strong electron donating group, Hammett plots showed slightly convoked characteristics which is similar to the plots of substituted benzenesulfonylchlorides, but contrary to the concaved nature for the halide exchange reactions of substituted benzyl chlorides. The rate of halogen exchange between benzenesulfonylbromide and lithium bromide decreased in the order of solvent : ($CH_3$)$_2$CO>$CH_3$CN》MeOH. The rates and activation parameters were also compared with those already known in the substituted benzenesulfonylchlorides. Theses were explained in terms of the structural properties of the transition state, and discussed the reaction mechanisms.s.

• Bulletin of the Korean Chemical Society
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• v.23 no.3
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• pp.404-412
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• 2002

Nine copper(Ⅱ) oxyanion, and mixed oxyanion complexes that have four- or five-coordinate geometries around copper(Ⅱ) centers were derived from sparteine copper(Ⅱ) dinitrate precursor [Cu($C_{15}$$H_{26}$N2)(NO3)2]. The precursor complex undergoes an anion exchange with various oxyanions, and an interchange reaction with other sparteine copper(Ⅱ) complexes. The [Cu($C_{15}$$H_{26}$N2)(CH3CO2)2] also undergoes "halogen atom abstraction" reaction with CCl4 to produce the mixed anion complex [Cu($C_{15}$$H_{26}$N2)(CH3CO2)Cl]. The whole set of prepared complexes has been used for the comparative electrochemical and spectroscopic studies.