Morpholinium Chloride Research Articles

A novel biomimetic probe for galectin‐3 recognition: Chemical synthesis and structural characterization of a β‐galactose branched sodium hyaluronate

AbstractSodium hyaluronate (HA), a derivative of hyaluronan, is a natural and biocompatible polysaccharide that interacts with cluster of differentiation‐44 receptor to promote fine‐tuning of inflammation, fibrosis, and tissue remodeling. HA has a smaller molecular weight than hyaluronan and is overall more stable being less prone to oxidation. In this study, we report a novel lactose‐functionalized sodium hyaluronate, named HYLACH®. Functionalization with multiple β‐galactose residues facilitates its interaction with galectin‐3, a β‐galactose binding lectin implicated in various pathological processes including inflammation, host defense, and fibrosis, especially critical in idiopathic pulmonary fibrosis (IPF). Our strategy was to modify HA, to varying extents, at carboxyl sites with 1‐amino‐1‐deoxy‐lactitol, in the presence of 4‐(4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl)‐4‐methyl morpholinium chloride in aqueous media. We characterized the chemical structure, molecular weight, and degree of substitution of HYLACH® using NMR spectroscopy and size exclusion chromatography. We further determined several key parameters including its stability toward enzymatic degradation and the binding affinity and conformational changes of galectin‐3 interaction with HYLACH®. Collectively, the generation of a novel functionalized HA with an ability to bind and suppress galectin‐3 function, in combination with safety and biocompatibility, offers the opportunity to test this compound in therapeutic trials of devastating fibrotic diseases such as IPF.

Structural characteristics and thermal properties of regenerated cellulose, hemicellulose and lignin after being dissolved in ionic liquids

This study investigated the use of ionic liquids such as 1-butyl-3-methylimidazolium chloride, 4-butyl-4-methyl morpholinium chloride, 1-butyl-1-methylpiperidinium chloride, and 1,3-dimethylimidazolium methylphosphite to dissolve cellulose, hemicellulose, and lignin biomass, as alternatives to highly toxic organic solvents. The biomass treated with the ionic liquids is characterized by scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and Fourier-transform infrared spectroscopy. The X-ray diffraction results revealed that most of the biomass treated with ionic liquids had low crystallinity after treatment with the ionic liquids. Thermogravimetric analysis confirmed that the pyrolysis temperature of the biomass treated with the ionic liquid decreased. However, it was found that the pyrolysis temperature of the biomass was increased again after the ionic liquid was washed with an antisolvent. This result was interpreted using Fourier-transform infrared spectroscopy to show that the O–H hydrogen bonding of cellulose was restored. The experimental results from this study can help provide a better understanding of the biomass regeneration mechanism of ionic liquids and increase the applicability of biomass in various fields.

Metal – organic hybrids of tin(IV) with tuneable band gap: Synthesis, spectral, single crystal X-ray structural, BVS and CSM analysis of morpholinium hexahalostannate(IV)

Self assembled organic - inorganic hybrid materials such as morpholinium hexachlorostannate(IV) (3) and morpholinium hexabromostannate(IV) (4) have been synthesised from morpholinium chloride (1) and morpholinium bromide (2) at room temperature. The hybrids were characterized by elemental analysis, IR, NMR, TG-DTA, DRS and PL spectroscopy and single crystal X-ray diffraction. IR and NMR spectral data of (3) and (4) show very little changes compared to their parent compounds (1) and (2). However, the = NH2+ proton signal of the bromide hybrid (4), shows a relatively lower δ value due to extensive hydrogen bonding compared to its chloride analogue (3). Thermal analysis confirmed the proposed formulae of the compounds. Optical absorption measurements showed 3.80 and 2.60 eV as band gaps for (3) and (4) respectively at room temperature implying that the band gaps can be easily tuned by altering the halide ion. Single crystal X-ray structures of compounds (3) and (4) revealed extensive hydrogen bonded interactions between the morpholinium cation and the SnCl62− and SnBr62− anions in (3) and (4). In (4), two molecules of morpholinium bromide co-crystallized with the hybrid. BVS calculations performed on SnCl62− and SnBr62− anions (3) and (4) resulted in 4.10 and 4.13 respectively, which clearly established the formal oxidation state of tin in the compounds as 4+. CSM calculation on SnBr62− yielded a value of 0.006 signifying a near perfect octahedral geometry of the anion.

Pyrrolidinium and morpholinium ionic liquids as a novel effective destabilising agent of mineral suspension

Here we describe ionic liquids (ILs) with an octyloxymethyl substituent in the cation designed and prepared using cheap and reactive cyclic tertiary amine: 1-methylpyrrolidine and 4-methylmorpholine. The synthesis rout was described, especially Menschutkin reaction. The physicochemical characteristics of the obtained pyrrolidinium and morpholinium chlorides were examined. The effect of the type of the amine present in the cation on the physicochemical properties of ionic liquids was determined. Next, the effect of these molecules on the stability of a quartz suspension was investigated. We found that an increase in the concentration of ILs in the suspension resulted in increased Turbiscan Stability Index (TSI) values by up to 64.7 and 65.9 for pyrrolidinium and morpholinium salts, respectively. The observed strong coagulation was a result of changes in the mineral surface properties due to the adsorption of the molecules. The ionic liquids molecules present at the quartz surface led to a more hydrophobic surface and changed the zeta potential value from −58.3 to −1.0 and 0.3 mV for pyrrolidinium chloride and morpholinium chloride, respectively. Our data show that these ionic liquid molecules could be used as effective, eco-friendly destabilising agents in the mineral industry.

A versatile post-polymerization modification method for polyglutamic acid: synthesis of orthogonal reactive polyglutamates and their use in “click chemistry”

In this article we describe a versatile methodology for the synthesis of polyglutamic acid (PGA) derivatives bearing orthogonal reactive sites. The reactive groups enable selective conjugation chemistry by copper catalyzed azide–alkyne coupling (CuAAC). PGA was derived in aqueous media as well as in organic media using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl morpholinium chloride (DMTTM) salts. The spectra of attached chemical moieties ranges from simple PEGylation with 2,5,8,11,14,17,20-heptaoxadocosan-22-amine (mEG(6)NH2) to the incorporation of propargylamine, 11-azido-3,6,9-trioxaundecan-1-amine (NH2-EG(2)N3), and 20-azido-3,6,9,12,15,18-hexaoxaicosan-1-amine (NH2-EG(6)N3). Herein, it is demonstrated that the degree of functionalization can be easily controlled within this one pot reaction. Additionally, we report conditions for the CuAAC with various PGA derivatives, which can be employed for site-specific conjugation of either hydrophilic or hydrophobic compounds.

ChemInform Abstract: Synthesis and Enantioselective Hydrogenation of Seven‐Membered Cyclic Imines: Substituted Dibenzo[b,f][1,4]oxazepines.

AbstractA highly enantioselective hydrogenation of cyclic imines such as (I) and (III) is achieved using an iridium‐based catalyst in combination with a chiral TunePhos bisphosphine ligand and morpholinium chloride.

Synthesis, Characterization, and Kinetic Study of Two New Cationic Surfactants

Abstract Two new surfactants (stearoyl morpholinium chloride and palmitoyl morpholinium chloride) were synthesized in two steps. In the first step, chloride acids were reacted with morpholine salt for producing morpholinium normal penta decyl ketone and morpholinium normal hepta decyl ketone. In the second step, the obtained products were reacted with HCl to produce suitable surfactants. The synthesis products in each steps were analyzed by Nuclear magnetic resonance (NMR), Fourier transform infrared spectrometry (FTIR), and elemental analysis. Also, the kinetic of the reactions were investigated. It has been shown that the synthesis reaction of the first step, the low rate step, follows a first order for two surfactants. The properties of two surfactants were investigated for anti-static and surface tension reduction. It was found that the hydrocarbon chain length is the main factor which has an effect on the properties of surfactants.

Synthesis of Non‐natural Xyloglucans by Polycondensation of 4,6‐Dimethoxy‐1,3,5‐triazin‐2‐yl Oligosaccharide Monomers Catalyzed by Endo‐β‐1,4‐glucanase

AbstractSummary: A cellotetraose‐backboned hepta‐saccharide (XXXG) (a capital X represents a glucopyranose residue that is substituted with a xylopyranose through an α‐1,6 glycosidic bond, and a capital G represents a non‐substituted glucopyranose residue) and a nona‐saccharide (XLLG) (a capital L represents a glucopyranose residue that is substituted with a galactopyranoseβ(1‐2)xylopyranose through an α‐1,6 glycosidic bond) have directly been converted to the corresponding 4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl derivatives (DMT‐β‐XXXG 1 and DMT‐β‐XLLG 2, respectively) by the action of 4‐(4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl)‐4‐methyl morpholinium chloride (DMT‐MM). The selective nucleophilic attack of the anomeric hydroxyl group to DMT‐MM has been achieved in water without using any protection of the hydroxyl groups. The resulting activated oligosaccharide derivatives (1 and 2) were found to polymerize catalyzed by an endo‐β‐1,4‐glucanase as catalyst. The polymerization took place in a complete regio‐ and stereo‐selective manner, affording non‐natural polysaccharides having a XXXG‐repeating unit and a XLLG‐repeating unit, respectively, in the main chain. It is extremely difficult to construct such definite repeating structures via the conventional synthetic routes including protection‐deprotection procedures.

Activation of Methylphosphonates and Their Thio- and Seleno Congeners with 1,3,5-Triazinyl Morpholinium Salts. Selenono-Selenolo Isomerization

The stereospecific activation of nucleoside 3′-O-methylphosphonoselenoates ( 1 ) with N-methyl-N-4,6-dimethoxy-1,3,5-triazinyl-yl morpholinium chloride resulted in formation of both O-activated (5) and Se-activated (6) 1,3,5-triazin-yl esters.

Analysis of structures with saturated hydrogen bonding

All simple structures with saturated hydrogen bonding (SHB) are classified into eight categories on the basis of the donor and acceptor numbers on the atoms at each end of the hydrogen bonds. Examples from the literature are included where known, along with seven structures investigated as part of this study (five have SHB). Graph-set descriptions of the hydrogen-bond patterns are given for each of these structures and for some selected literature examples. The structures presented are: piperazine (I), morpholinium chloride (II) and iodide (III) [(II) and (III) are not SHB], three 1:1 cocrystals of diols with 1,4-phenylenediamine (PDA)--PDA.1,8-octane diol (IV), PDA.1,10-decane diol (V), and PDA.1,12-dodecane diol (VI) and 6-amino-1-hexanol (VII). This study discusses some structures that show limitations of the graph-set model, along with possible suggestions to cover these limitations. The cocrystalline PDA.aliphatic diol structures may provide details applicable to the structure of self-assembled monolayers of aliphatic thiol molecules on Au(111) surfaces.

A universal approach to the synthesis of carbohydrate conjugates of polyhedral boron compounds as potential agents for boron neutron capture therapy

A uniform approach to the synthesis of carbohydrate conjugates with polyhedral boron compounds (PBCs) was developed. Oligosaccharide derivatives with an aglycone moiety amino group can be coupled with PBC carboxyl derivatives using N-methyl-N-(4,6-dimethoxy-1,3,5-triazin-2-yl)morpholinium chloride as a coupling agent. Both N- and O-glycosides differing in the conformational mobility around the glycoside bond were shown to be useful as oligosaccharides with a functional group in the aglycone moiety. This allows the application of this approach to the synthesis of PBC conjugates with a wide range of oligosaccharides. For example, not only oligosaccharides obtained by chemical synthesis but also reducing oligosaccharides isolated from natural sources can be transformed into N-glycosides. The approach was tested by the example of conjugation of the carboxyl derivatives of ortho-carborane and dodecaborate anion with lactose as a model oligosaccharide. Lactose, an easily available disaccharide, is a ligand for lectins expressed on the surface of melanoma cells. The approach suggested is the first example of the synthesis of such conjugates that does not require protective groups for the carbohydrate residue. It is especially important for obtaining dodecaborate-carbohydrate conjugates for which the removal of protective groups is often a non-trivial task.

Spectroscopic and structural properties of some N-(2-hydroxyethyl)-morpholine derivatives

The 1H, 13C and 15N NMR spectra of N-(2-hydroxyethyl)-morpholine ( 1), N-(2-hydroxyethyl)-morpholinium chloride ( 2), N-(2-hydroxyethyl)-morpholine betaine ( 3), N-morpholinyl-spiro-morpholactone chloride ( 4) and N-morpholinyl-spiro-morpholactone picrate ( 5) have been recorded and analyzed. The influence of protonation and N-alkylation of morpholine is discussed. The crystal structures of 4 and 5 have been determined by X-ray diffraction: 4 is orthorhombic, space group Pna2 1 and 5 is monoclinic, space group P2 1/ c. The structure of 5 is well reproduced by the PM3 and SAM1 methods.

Spectroscopic and structural properties of some N-(2-hydroxyethyl)-morpholine derivatives

The 1 H, 13 C and 15 N NMR spectra of N -(2-hydroxyethyl)-morpholine ( 1 ), N -(2-hydroxyethyl)-morpholinium chloride ( 2 ), N -(2-hydroxyethyl)-morpholine betaine ( 3 ), N -morpholinyl-spiro-morpholactone chloride ( 4 ) and N -morpholinyl-spiro-morpholactone picrate ( 5 ) have been recorded and analyzed. The influence of protonation and N-alkylation of morpholine is discussed. The crystal structures of 4 and 5 have been determined by X-ray diffraction: 4 is orthorhombic, space group Pna 2 1 and 5 is monoclinic, space group P 2 1 / c . The structure of 5 is well reproduced by the PM3 and SAM1 methods.

Thermodynamic Properties of Aqueous Morpholine and Morpholinium Chloride at Temperatures from 10 to 300 °C: Apparent Molar Volumes, Heat Capacities, and Temperature Dependence of Ionization

Apparent molar heat capacities Cp,φ of aqueous morpholine and morpholinium chloride were determined with a Picker flow microcalorimeter at temperatures from 10 to 55 °C. The apparent molar volumes Vφ have been determined with platinum vibrating tube densitometers at temperatures from 10 to 300 °C and pressures in excess of steam saturation. Values of Vφ for morpholine approach large positive values at elevated temperatures, consistent with a lowering of the critical temperature in the solutions relative to water. The effect in aqueous morpholinium chloride is reversed, confirming the profound effect of ionic charge on the high-temperature thermodynamic properties of aqueous solutes, even for large organic molecules. Standard partial molar heat capacity functions were estimated from the high-temperature Vφ data and low-temperature values of Cp,φ using an empirical model based on the appropriate solvent density derivatives and the revised Helgeson−Kirkham−Flowers model. The results from both models are consistent with literature values for the heat capacity of ionization determined from high-temperature potentiometric measurements to within the combined experimental uncertainties. The results show that the effects of solvent expansion by the neutral species is significant at elevated temperatures. The effective Born radius of ions containing organic groups could be significantly larger than the radius calculated from the formula for simple cations because of this effect.

Antistatische Eigenschaften von Pyrrolidinium-, Morpholinium- und Pyridinium-Chloriden mit Alkoxymethylund Alkylthiomethylrest/ Antistatic Properties of Pyrrolidinium-, Morpholinium and Pyridinium Chlorides with Alkoxy Methyl and Alkyl Thiomethyl Radicals

The antistatic properties of the following compounds were investigated: 1-alkoxymethyl- and 1-alkylthiomethyl-1-methylpyrrolidinium chloride, 4-alkylthiomethyl-4-dodecyl- and 4-alkyl thiomethyl-4-(2'-hydroxyethyl))morpholinium chloride, 1-alkylthiomethyl- and 1-alkoxymethyl-3-ethoxymethylpyridinium chloride and 1-alkyl thiomethyl-3-butyl thiomethyl pyridinium chloride. It was found that of the 58 chlorides examined, no fewer than 28 possess excellent antistatic properties.

Micellization of some amphiphilic quaternary ammonium chlorides

The micellization processes of N-dodecyl- N,N-dimethyl- N-[3-(β-methyl-β-nitrovinyl)-6-methoxybenzyl] ammonium chloride ( I-A), N-dodecyl- N,N-dimethyl- N-benzylammonium chloride ( I-B), N-dodecyl- N, N,N-trimethylammonium chloride ( I-C), N-dodecyl-[3-(β-methyl-β-nitrovinyl)-4-methoxybenzyl] morpholinium chloride ( IV-A), N-dodecyl- N-benzylmorpholinium chloride ( IV-B), N-dodecyl- N-methylmorpholinium chloride ( IV-C), and N-dodecyl- N-methylpiperidinium chloride ( VI-C) were studied by means of the calorimetric titration method. The critical micelle concentrations and enthalpies of micellization were determined. It is suggested that the benzyl groups of I-B and IV-B and the nitrovinylbenzyl groups of I-A and IV-A behave as second chains during the micellization.

Synthesis of N,N‐dimethyl[2‐14C] morpholinium chloride

AbstractN,N‐dimethyl [2‐14C] morpholinium chloride was obtained from [1‐14C] acetic acid in five‐step synthesis with [2‐14C] morpholine as the intermediate.

Thermodynamics of the dissociation of morpholinium ion in seawater from 5 to 40�C

The dissociation constant of morpholinium ion has been determined in five synthetic seawaters at eight temperatures from 5 to 40°C. The seawater solvents contained NaCl, MgCl2, Na2SO4, CaCl2, and KCl in amounts corresponding to salinities of approximately 10, 20, 30, 35, and 40‰ (parts per thousand) and ionic strengths ranging from 0.2 to 0.8 mol-kg−1. Electromotive-force measurements of cells without liquid junction, with hydrogen gas electrodes and Ag/AgCl electrodes, were used to derive the dissociation constant and associated changes of enthalpy, entropy, and heat capacity for the dissociation equilibrium. The pK values over the range of salinity S and thermodynamic temperature T studied are given by the equation $$\begin{gathered} pK = (1396.58 + 1.822S)/T - 2.14236 InT + 16.0138 + 0.001912S \hfill \\ - 9.722 \times 10^{ - 5} S^2 + 1.025 \times 10^{ - 6} S^3 \hfill \\ \end{gathered}$$ At a salinity of 35‰, corresponding to ‘normal seawater’, pK is higher by 0.206 at 25°C than in the water solvent, while ΔHo is increased by 292 cal-mol−1 and both ΔSo and ΔC p o are substantially unchanged. The buffer composed of 0.04 molal morpholinium chloride and 0.04 molal morpholine is useful for pH control in synthetic seawater media.

ChemInform Abstract: FORMATION AND REACTIONS OF ALKOXYDIAMINOSULFONIUM SALTS

AbstractDas Äthoxydimorpho‐ linosulfonium‐tetrafluoroborat (III) wird durch Äthylierung des Sulfoxids (I) mit dem Oxonium‐Salz (II) synthetisiert.

Formation and Reactions of Alkoxydiaminosulfonium Salts

Abstract Ethoxydimorpholinosulfonium tetrafluoroborate and tetraphenylborate were prepared by ethylation of dimorpholino sulfoxide. They were readily hydrolyzed with water but did not react with methanol. In the reactions with nucleophiles, they acted as ethylating agent for β-picoline, triethylamine, diethylamine, methoxide ion, and chloride ion. When dimorpholino sulfide, 1-chlorobenzotriazole, and an alcohol were allowed to react at −80 °C, the main products were an alkyl chloride, dimorpholino sulfoxide, and morpholinium chloride. Alkoxydimorpholinosulfonium chloride was presumed to be the intermediate, which decomposed by an SN2-type nucleophilic attack of chloride ion on the alkyl group. When (+)-2-octanol was used, the 2-chlorooctane formed was of almost completely inverted configuration (enantiomeric excess, 97%). The yield of alkyl chlorides decreased in the order of methyl (80%), isopropyl (51), and t-butyl (20).