69709-39-3Relevant academic research and scientific papers
Substituent effects on the electrophilic activity of nitroarenes in reactions with carbanions
Blazej, Sylwia,Makosza, Mieczyslaw
supporting information; experimental part, p. 11113 - 11122 (2009/11/30)
The effect on electrophilic activity of substituents located para, ortho, and meta to the nitro group of nitrobenzenes was determined by using vicarious nucleophilic substitution of hydrogen (VNS) with the carbanion of chloromethyl phenyl sulfone (1) as the model process. Values for the relative activities of substituted nitroarenes are given relative to nitrobenzene, which was taken as the standard. This process was chosen as a model reaction because it meets key criteria, such as the wide range of substituents that can be present on the nitrobenzene ring, a low sensitivity to steric hindrance, and in particular the possibility of ensuring conditions in which the overall relative rates of reaction in competitive experiments are equal to the relative rates of nucleophilic addition. The values of relative rates of addition, which were taken to be a measure of electrophilic activity, were determined by competitive experiments in which pairs of nitroarenes competed for the VNS reaction with carbanion of 1. A comprehensive set of data for effects of substituents on the electrophilic activity of nitroarenes is presented for the first time.
Reactions of nitroheteroarenes with carbanions: Bridging aromatic, heteroaromatic and vinylic electrophilicity
Seeliger, Florian,Blazej, Sylwia,Bernhardt, Sebastian,Makosza, Mieczyslaw,Mayr, Herbert
supporting information; experimental part, p. 6108 - 6118 (2009/07/18)
The relative rate constants for the vicarious nucleophilic substitution (VNS) of the anion of chloromethyl phenyl sulfone (1-) with a variety of nitroheteroarenes, for example, nitropyridines, nitropyrroles, nitroimidazoles, 2-nitrothiophene, and 4-nitropyrazole, have been determined by competition experiments. It was shown that nitropyridines are approximately four orders of magnitude more reactive than nitrobenzene. Among the five-membered heterocycles 2-nitrothiophene is the most active followed by nitroimidazoles and 4-nitropyrazole. Nitropyrroles are the least electrophilic nitroheteroarenes with reactivities comparable to nitrobenzene. Quantum chemically calculated methyl anion affinities (B3LYP/6-311 G(d,p)//B3LYP/ 6-31G(d)) of the nitroarenes correlated only moderately with the partial relative rate constants. The correlation of these activities with the LUMO energies of nitroarenes is even worse. By measuring the second-order rate constants of the addition of 1" to nitroarenes and to diethyl arylidenemalonates 10, it was possible to link the electrophilic reactivities of nitroheteroarenes with the comprehensive electrophilicity scale based on the linear-free-energyrelationship log k(20°C) = s(N + E).
1-(2-Aminoethyl)-3-(arylsulfonyl)-1H-indoles as novel 5-HT6 receptor ligands
Bernotas, Ronald,Lenicek, Steven,Antane, Schuyler,Zhang, Guo Ming,Smith, Deborah,Coupet, Joseph,Harrison, Boyd,Schechter, Lee E.
, p. 5499 - 5502 (2007/10/03)
Novel 1-(2-aminoethyl)-3-(arylsulfonyl)-1H-indoles were prepared. Binding assays indicated they are 5-HT6 receptor ligands, among which N,N-dimethyl-N-{2-[3-(1-naphthylsulfonyl)-1H-indol-1-yl]ethyl}amine 8t and N-methyl-N-{2-[3-(1-naphthylsulfonyl)-1H-indol-1-yl]ethyl}amine 8u showed high affinity for 5-HT6 receptors with Ki = 3.7 and 5.7 nM, respectively. Novel 1-(2-aminoethyl)-3-(arylsulfonyl)-1H-indoles were prepared. Binding assays indicated they are 5-HT6 receptor ligands, among which N,N-dimethyl-N-{2-[3-(1-naphthylsulfonyl)-1H-indol-1-yl]ethyl}amine 8t and N-methyl-N-{2-[3-(1-naphthylsulfonyl)-1H-indol-1-yl]ethyl}amine 8u showed high affinity for 5-HT6 receptors with Ki = 3.7 and 5.7 nM, respectively.
1-(AMINOALKYL)-3-SULFONYLINDOLE AND-INDAZOLE DERIVATIVES AS 5-HYDROXYTRYPTAMINE-6 LIGANDS
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Page 12, (2010/02/05)
The present invention provides compounds of formula I and the use thereof for the treatment of central nervous system disorders related to or affected by the 5-HT6 receptor.
Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes with Carbanions of α-Haloalkyl Phenyl Sulfones
Makosza, Mieczyslaw,Golinski, Jerzy,Baran, Janusz
, p. 1488 - 1494 (2007/10/02)
Carbanions of α-chloroalkyl phenyl sulfones and N,N-dialkyl-α-chloroalkanesulfonamides react with nitrobenzenes to effect direct nucleophilic replacement of hydrogen ortho and para to the nitro group, with vicarious loss of chloride anion, to give the corresponding nitrobenzylsulfonyl derivatives.The reaction occurs much more rapidly than the replacement of such good leaving groups as halogen, methoxy, and phenoxy.Most substituents in the nitrobenzene ring do not interfere with the reaction.The effect of substituents in the nitrobenzene and the carbanion on the orientation of the substitution is discussed.
