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91.
Methylation of the anionic 4-methylcarboxy 1,2,3-oxadiazolate 3-oxide occurs at either the disubstituted ring nitrogen or the oxygen of the N-oxide depending upon the conditions and reagents employed. Alkylation with methyl iodide leads to N-alkylation, while dimethyl sulfate gives O-alkylation and trifluoromethanemethylsulfonate gives a mixture of the two products. The regioselectivity of these methylations has been confirmed by X-ray diffraction of the two products, and these are in turn correlated with their theoretically predicted (B3LYP//6-311++G**) relative energies and vibrational spectra. Theoretically, N-alkylation is expected to give an isomer that is over 10 kcal mol-1 more stable than the O-alkylated product. As a neat melt the kinetic O-alkylation product cleanly isomerizes in 2 h when heated to 140 degrees C to give the thermodynamic N-methylated isomer. Taken together the results illustrate the remarkable new sydnone N-oxide derivatives which are readily accessed in this chemistry, with the N-alkylation of the sydnone N-oxide, corresponding to the first case of such an N-alkylation for a diazenium diolate. 相似文献
92.
Gutzler R Ivasenko O Fu C Brusso JL Rosei F Perepichka DF 《Chemical communications (Cambridge, England)》2011,47(33):9453-9455
We report the formation of highly-ordered self-assembled monolayers of an achiral organic semiconductor molecule. STM results show spontaneous formation of very large single domains of ordered chiral monolayers. DFT calculations support the identification of halogen bonds as the primary interactions that steer molecular self-assembly, leading to organizational chirality. 相似文献
93.
Muhammad Ghufran Rafique Dr. Jacob M. Remington Finley Clark Haochen Bai Dr. Violeta Toader Prof. Dmytro F. Perepichka Prof. Jianing Li Prof. Hanadi F. Sleiman 《Angewandte Chemie (International ed. in English)》2023,62(24):e202217814
Two-dimensional (2D) assemblies of water-soluble block copolymers have been limited by a dearth of systematic studies that relate polymer structure to pathway mechanism and supramolecular morphology. Here, we employ sequence-defined triblock DNA amphiphiles for the supramolecular polymerization of free-standing DNA nanosheets in water. Our systematic modulation of amphiphile sequence shows the alkyl chain core forming a cell membrane-like structure and the distal π-stacking chromophore block folding back to interact with the hydrophilic DNA block on the nanosheet surface. This interaction is crucial to sheet formation, marked by a chiral “signature”, and sensitive to DNA sequence, where nanosheets form with a mixed sequence, but not with a homogeneous poly(thymine) sequence. This work opens the possibility of forming well-ordered, bilayer-like assemblies using a single DNA amphiphile for applications in cell sensing, nucleic acid therapeutic delivery and enzyme arrays. 相似文献