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The role of N-substitution on 2-aminothiazole [2AT], N-methylthio-N’-2-amino-5-mercapto-1,3,4-thiadiazole [2AMT] and 2-aminobenzothiazole [2ABT] in room-temperature ionic liquids was investigated. For this purpose, 2AMT was analyzed by NMR and LC-MS at different temperatures. In a room-temperature ionic liquid (RTIL) 1-Butyl-3-methylimidazolium tetrafluoroborate [BMIM BF4], 2ABT exists predominantly as a mixture of 1-butyl-3-methylimidazolium thiocyanate [BMIM SCN] and 1-butyl-3-methylimidazolium dicyanamide [BMIM NCN]. However, in an aprotic solvent (dichloroethane), the isolated structure of 2ABT could be obtained, and this was confirmed by X-ray diffraction. Moreover, 2AMT was found to exist predominantly as an unsymmetrical dimer in BMIM BF4 and as a mixture of monomer and dimer in dichloroethane. On the basis of the findings, it was concluded that the polar head group and the alkyl chain in RTILs play a vital role in the formation of the structures of 2AT
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