An NMR study of quaternary ammonium salts of 5,7-dimethyl-1,3-diazaadamantan-6-one

Semashko, V. S.; Вацадзе, С. З.; Зык, Н. В.; Godovikov, Ivan A.

doi:10.1007/s11172-008-0303-5

Cited by 4 publications

(3 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Upon heating to 60 °C, the ratio changes to ∼1.8:1.0, reducing to the starting position after cooling to rt (Figure 4). An analogous hydration reaction was described for quaternary ammonium salts of 5,7-dimethyl-1,3-diazaadamantan-6-one in D 2 O 50 and for bispidine platinum complexes. 51 Commonly, the behavior of compound 3b in D 2 O is similar (Figure S31) to that of the glycine analogue, 2b , described above.…”

Section: Results and Discussionmentioning

confidence: 88%

Copper–Bispidine Complexes: Synthesis and Complex Stability Study

et al. 2016

View full text Add to dashboard Cite

A new series of dicarboxylic derivatives of bispidines have been synthesized to develop novel copper(II) complexes suitable as imaging agents for positron emission tomography. For characterization purposes, copper complexes of bispidines were synthesized in the pure form and in quantitative yields by neutralization of ligands with malachite. The formation of complexes and their stoichiometries were studied by potentiometric titration, cyclic voltammetry, and spectroscopic methods. The stability constants were found to be fairly suitable for copper cation fixation inside dianionic chelate molecules.

show abstract

Section: Results and Discussionmentioning

confidence: 88%

Copper–Bispidine Complexes: Synthesis and Complex Stability Study

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Compounds 1 – 3 were prepared according to protocols from [24,55,56]: the stereoselective ring opening in salts 1 leads to unsymmetrically substituted bispidinols 2 ; the deformylation of the latter gives rise to secondary amino alcohols 3 (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Supramolecular Organogels Based on N-Benzyl, N′-Acylbispidinols

et al. 2019

View full text Add to dashboard Cite

The acylation of unsymmetrical N-benzylbispidinols in aromatic solvents without an external base led to the formation of supramolecular gels, which possess different thicknesses and degrees of stability depending on the substituents in para-positions of the benzylic group as well as on the nature of the acylating agent and of the solvent used. Structural features of the native gels as well as of their dried forms were studied by complementary techniques including Fourier-transform infrared (FTIR) and attenuated total reflection (ATR) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and small-angle X-ray scattering and diffraction (SAXS). Structures of the key crystalline compounds were established by X-ray diffraction. An analysis of the obtained data allowed speculation on the crucial structural and condition factors that governed the gel formation. The most important factors were as follows: (i) absence of base, either external or internal; (ii) presence of HCl; (iii) presence of carbonyl and hydroxyl groups to allow hydrogen bonding; and (iv) presence of two (hetero)aromatic rings at both sides of the molecule. The hydrogen bonding involving amide carbonyl, hydroxyl at position 9, and, very probably, ammonium N-H+ and Cl− anion appears to be responsible for the formation of infinite molecular chains required for the first step of gel formation. Subsequent lateral cooperation of molecular chains into fibers occurred, presumably, due to the aromatic π−π-stacking interactions. Supercritical carbon dioxide drying of the organogels gave rise to aerogels with morphologies different from that of air-dried samples.

show abstract

“…Compounds 1-3 were prepared according to protocols from [24,55,56]: the stereoselective ring opening in salts 1 leads to unsymmetrically substituted bispidinols 2; deformylation of the later gives rise to secondary amino alcohols 3 (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols

Медведько

Dalinger

Nuriev

et al. 2018

Preprint

View full text Add to dashboard Cite

The acylation of unsymmetrical N-benzylbispidinols in aromatic solvents without external base led to formation of supramolecular gels, which possess different thickness and stability depending on the substituents in para-positions of benzylic group and nature of acylating agent as well as on the nature of the solvent used. Structural features of the native gels as well as of their dried forms were studied by complementary techniques including FT IR-and ATR-spectroscopy, AFM, TEM, SEM, SAXS. Structures of the key crystalline compounds were established by X-ray diffraction. Analysis of obtained data allowed speculating on the crucial structural and condition factors that governed the gel formation. The most important factors were: (i) absence of base, either external or internal; (ii) presence of HCl; (iii) presence of carbonyl and hydroxyl groups to allow hydrogen bonding; (iv) presence of two (hetero)aromatic rings at both sides of the molecule. The hydrogen bonding involving amide carbonyl, hydroxyl at 9 th position and, very probably, ammonium N-H+ and Cl-anion appear to be responsible for the formation of infinite molecular chains required for the first step of gel formation. Subsequent lateral cooperation of molecular chains into fibers occured, presumably, due to the aromatic pi-pi-stacking interactions. sc-CO2 drying of the gels gave rise to aerogels morphology different from that of air dried samples. requires use of poly/multifunctional chelating agents that should form covalent bonds with various biomolecules/vectors possessing high specificity and selectivity towards certain targets [5], [8][9][10][11]. 3,7-Diazabicyclo[3.3.1]nonanes (hereafter called bispidines) are one of the privileged scaffolds in medicinal chemistry [12] due to the number of advantages, e.g. (i) high basicity and solubility in water and/or organic solvents [13,14]; (ii) ability to diverse functionalization including chiral derivatives [15][16][17][18][19][20]; (iii) deeply studied conformational features which allow application of some rigid conformation [21][22][23]. Our recent works have shown potential of using the bispidine scaffolds for design of inhibitors of serine proteases [24,25]. At the same time, bispidines are well-known ligands with high affinity to Cu(II) and some other bivalent metals [26][27][28][29]. Therefore, we focus on creating new potent ligands for 64 Cu PET based on number of unsymmetrically substituted bispidine-9-ols. During our work with ligands for serine proteases it was necessary to find a way to insert bulky groups into pockets of the active site [24,25]. The acylation reaction is one of the obvious ways to functionalize the secondary amine group in N-benzylbispidinols; the resulting N-benzyl, N'-acylbispidinols allow subsequent transformations like reduction of amide group or removal of the protecting benzylic group followed by diverse functionalization of the formed secondary amine. In the course of our work we have discovered an interesting phenomenon, namely, formation of gels during the acylatio...

show abstract

An NMR study of quaternary ammonium salts of 5,7-dimethyl-1,3-diazaadamantan-6-one

Abstract: The temperature dependence of the 1 H NMR spectra of quaternary ammonium salts of 5,7 dimethyl 1,3 diazaadamantan 6 one in D 2 O was examined. The molar ratio of the ketone and hydrate forms was determined.

Cited by 4 publications

References 5 publications

Copper–Bispidine Complexes: Synthesis and Complex Stability Study

Copper–Bispidine Complexes: Synthesis and Complex Stability Study

Supramolecular Organogels Based on N-Benzyl, N′-Acylbispidinols

Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols

Contact Info

Product

Resources

About

An NMR study of quaternary ammonium salts of 5,7-dimethyl-1,3-diazaadamantan-6-one

Abstract: The temperature dependence of the 1 H NMR spectra of quaternary ammonium salts of 5,7 dimethyl 1,3 diazaadamantan 6 one in D 2 O was examined. The molar ratio of the ketone and hydrate forms was determined.

Cited by 4 publications

References 5 publications

Copper–Bispidine Complexes: Synthesis and Complex Stability Study

Copper–Bispidine Complexes: Synthesis and Complex Stability Study

Supramolecular Organogels Based on N-Benzyl, N′-Acylbispidinols

Supramolecular Organogels Based on N-Benzyl, N&rsquo;-Acylbispidinols

Contact Info

Product

Resources

About

Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols