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18 pages, 2334 KiB

Open AccessArticle

Solvent-Impregnated Resins Based on the Mixture of (2-Diphenylphosphoryl)-4-ethylphenoxy)methyl) diphenylphosphine Oxide and Ionic Liquid for Nd(III) Recovery from Nitric Acid Media

by Olga Kovalenko, Vladimir Baulin, Dmitriy Baulin and Aslan Tsivadze

Molecules 2021, 26(9), 2440; https://doi.org/10.3390/molecules26092440 - 22 Apr 2021

Cited by 4 | Viewed by 2099

Abstract

Novel solvent-impregnated resins (SIRs) were prepared by treatment of styrene–divinylbenzene copolymer (LPS-500) with mixtures of the promising polydentante extractant (2-diphenylphosphoryl)-4-ethylphenoxy)methyl)diphenylphosphine oxide (L) and an ionic liquid [C₄mim]⁺[Tf₂N]⁻for the extraction chromatography recovery of Nd(III) from nitric [...] Read more.

Novel solvent-impregnated resins (SIRs) were prepared by treatment of styrene–divinylbenzene copolymer (LPS-500) with mixtures of the promising polydentante extractant (2-diphenylphosphoryl)-4-ethylphenoxy)methyl)diphenylphosphine oxide (L) and an ionic liquid [C₄mim]⁺[Tf₂N]⁻for the extraction chromatography recovery of Nd(III) from nitric acid solutions. It was shown that introduction of the ionic liquid into the SIR composition results in considerable enhancement of the Nd(III) recovery efficiency compared with resin impregnated only by L in slightly acidic media. The influence of the L: ionic liquid molar ratio in the SIRs composition, their percentages, concentration of metal and HNO₃ in the eluent, and acid type on the value of synergistic effect and adsorption efficiency of Nd(III) recovery was studied. The SIR containing 40% of mixture of L and [C₄mim]⁺[Tf₂N]⁻ with molar ratio 2:1 turned out to be the most efficient. The selectivity of Nd(III) separation from light and heavy rare-earth elements was studied and the optimal conditions of Nd(III) adsorption recovery and stripping by this SIR were chosen. It was found that in recovery efficiency of Nd(III) developed SIR exceeded the SIR containing Cyanex 923 (a mixture of monodentate trialkylphosphine oxides) and [C₄mim]⁺[Tf₂N]⁻. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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14 pages, 1079 KiB

Open AccessArticle

Synthesis, Complexation Properties, and Evaluation of New Aminodiphosphonic Acids as Vector Molecules for ⁶⁸Ga Radiopharmaceuticals

by Alesya Ya. Maruk, Valery V. Ragulin, Iurii A. Mitrofanov, Galina S. Tsebrikova, Vitaly P. Solov’ev, Alexandr S. Lunev, Kristina A. Lunyova, Olga E. Klementyeva, Vladimir E. Baulin, Galina E. Kodina and Aslan Yu. Tsivadse

Molecules 2021, 26(8), 2357; https://doi.org/10.3390/molecules26082357 - 18 Apr 2021

Cited by 2 | Viewed by 2134

Abstract

Two new aminodiphosphonic acids derived from salicylic acid and its phosphonic analogue were prepared through a simple and efficient synthesis. 2-[(2-Amino-2,2-diphosphono)ethyloxy]-benzoic acid 8 and 2-[(2-amino-2,2-diphosphono)ethyloxy]-5-ethyl-phenylphosphonic acid 9 were evaluated for their applicability as ⁶⁸Ga binding bone-seeking agents. Protonation constants of 8 and [...] Read more.

Two new aminodiphosphonic acids derived from salicylic acid and its phosphonic analogue were prepared through a simple and efficient synthesis. 2-[(2-Amino-2,2-diphosphono)ethyloxy]-benzoic acid 8 and 2-[(2-amino-2,2-diphosphono)ethyloxy]-5-ethyl-phenylphosphonic acid 9 were evaluated for their applicability as ⁶⁸Ga binding bone-seeking agents. Protonation constants of 8 and 9 and stability constants of the Ga³⁺ complexes with 8 and 9 in water were determined. The stability constant of Ga³⁺ complex with fully phosphorylated acid 9 (logK_GaL = 31.92 ± 0.32) significantly exceeds stability constant of Ga³⁺ complex with 8 (logK_GaL = 26.63 ± 0.24). Ligands 8 and 9 are as effective for Ga³⁺ cation binding as ethylenediamine-N,N’-diacetic-N,N’-bis(methy1enephosphonic) acid and ethylenediamine-N,N,N’,N’-tetrakis(methylenephosphonic) acid, respectively. The labelling process and stability of [⁶⁸Ga]Ga-8 and [⁶⁸Ga]Ga-9 were studied. Both 8 and 9 readily form ⁶⁸Ga-complexes stable to ten-fold dilution with saline. However, in fetal bovine serum, only [⁶⁸Ga]Ga-9 was stable enough to be subject to biological evaluation. It was injected into rats with bone pathology and aseptic inflammation of soft tissues. For [⁶⁸Ga]Ga-9 in animals with a bone pathology model in 60 and 120 min after injection, a slight accumulation in the pathology site, stable blood percentage level, and moderate accumulation in the liver were observed. For animals with an aseptic inflammation, the accumulation of [⁶⁸Ga]Ga-9 in the pathology site was higher than that in animals with bone pathology. Moreover, the accumulation of [⁶⁸Ga]Ga-9 in inflammation sites was more stable than that for [⁶⁸Ga]Ga-citrate. The percentage of [⁶⁸Ga]Ga-9 in the blood decreased from 3.1% ID/g (60 min) to 1.5% ID/g (120 min). Accumulation in the liver was comparable to that obtained for [⁶⁸Ga]Ga-citrate. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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24 pages, 7218 KiB

Open AccessArticle

Design of Extractants for F-Block Elements in a Series of (2-(Diphenylphosphoryl)methoxyphenyl)diphenylphosphine Oxide Derivatives: Synthesis, Quantum-Chemical, and Extraction Studies

by Alfiya Safiulina, Nataliya Borisova, Mikhail Grigoriev, Dmitriy Baulin, Vladimir Baulin and Aslan Tsivadze

Molecules 2021, 26(8), 2217; https://doi.org/10.3390/molecules26082217 - 12 Apr 2021

Cited by 2 | Viewed by 1809

Abstract

With the aim to find new efficient extractants for recovery of f-block elements from processing wastes of different origin, we have compared a series of phosphoryl-containing podands, including (2-(diphenylphosphorylmethoxy)phenyl)diphenylphosphine oxide 1 and its analogues 5–7, where the ArP(O)Ph₂ group [...] Read more.

With the aim to find new efficient extractants for recovery of f-block elements from processing wastes of different origin, we have compared a series of phosphoryl-containing podands, including (2-(diphenylphosphorylmethoxy)phenyl)diphenylphosphine oxide 1 and its analogues 5–7, where the ArP(O)Ph₂ group of phosphine oxide type is replaced by phosphonic fragments. Quantum-chemical modelling of the structures of phosphoryl-containing podands 1 and 5–7 has been performed, which was later confirmed by the data of X-ray diffraction. The features of extraction of nitric acid, as well as U(VI), Th(IV), Nd(III), and Ho(III) with compounds 1 and 5–7 from nitric acid media into 1,2-dichloroethane have been studied. The compositions of extracted complexes have been determined. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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14 pages, 5105 KiB

Open AccessArticle

N-Benzyl Residues as the P1′ Substituents in Phosphorus-Containing Extended Transition State Analog Inhibitors of Metalloaminopeptidases

by Kamila Janiszewska, Michał Talma, Bartosz Oszywa, Małgorzata Pawełczak, Paweł Kafarski and Artur Mucha

Molecules 2020, 25(18), 4334; https://doi.org/10.3390/molecules25184334 - 22 Sep 2020

Cited by 1 | Viewed by 2405

Abstract

Peptidyl enzyme inhibitors containing an internal aminomethylphosphinic bond system (P(O)(OH)-CH₂-NH) can be termed extended transition state analogs by similarity to the corresponding phosphonamidates (P(O)(OH)-NH). Phosphonamidate pseudopeptides are broadly recognized as competitive mechanism-based inhibitors of metalloenzymes, mainly hydrolases. Their practical use is, [...] Read more.

Peptidyl enzyme inhibitors containing an internal aminomethylphosphinic bond system (P(O)(OH)-CH₂-NH) can be termed extended transition state analogs by similarity to the corresponding phosphonamidates (P(O)(OH)-NH). Phosphonamidate pseudopeptides are broadly recognized as competitive mechanism-based inhibitors of metalloenzymes, mainly hydrolases. Their practical use is, however, limited by hydrolytic instability, which is particularly restricting for dipeptide analogs. Extension of phosphonamidates by addition of the methylene group produces a P-C-N system fully resistant in water conditions. In the current work, we present a versatile synthetic approach to such modified dipeptides, based on the three-component phospha-Mannich condensation of phosphinic acids, formaldehyde, and N-benzylglycines. The last-mentioned component allowed for simple and versatile introduction of functionalized P1′ residues located on the tertiary amino group. The products demonstrated moderate inhibitory activity towards porcine and plant metalloaminopeptidases, while selected derivatives appeared very potent with human alanyl aminopeptidase (K_i = 102 nM for 6a). Analysis of ligand-protein complexes obtained by molecular modelling revealed canonical modes of interactions for mono-metallic alanyl aminopeptidases, and distorted modes for di-metallic leucine aminopeptidases (with C-terminal carboxylate, not phosphinate, involved in metal coordination). In general, the method can be dedicated to examine P1′-S1′ complementarity in searching for non-evident structures of specific residues as the key fragments of perspective ligands. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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17 pages, 4616 KiB

Open AccessFeature PaperArticle

Study on the Microwave-Assisted Batch and Continuous Flow Synthesis of N-Alkyl-Isoindolin-1-One-3-Phosphonates by a Special Kabachnik–Fields Condensation

by Ádám Tajti, Nóra Tóth, Bettina Rávai, István Csontos, Pál Tamás Szabó and Erika Bálint

Molecules 2020, 25(14), 3307; https://doi.org/10.3390/molecules25143307 - 21 Jul 2020

Cited by 11 | Viewed by 2860

Abstract

A simple and efficient microwave (MW)-assisted method was elaborated for the catalyst-free synthesis of isoindolin-1-one-3-phosphonates by the three-component condensation of 2-formylbenzoic acid, aliphatic primary amines and various dialkyl phosphites. The batch and the continuous flow reactions were optimized in respect of the temperature, [...] Read more.

A simple and efficient microwave (MW)-assisted method was elaborated for the catalyst-free synthesis of isoindolin-1-one-3-phosphonates by the three-component condensation of 2-formylbenzoic acid, aliphatic primary amines and various dialkyl phosphites. The batch and the continuous flow reactions were optimized in respect of the temperature, the reaction time and the molar ratio of the starting materials. To evaluate the potential of MW irradiation, comparative thermal experiments were also carried out. In order to obtain “real time” information about the condensation, the special Kabachnik–Fields reaction of 2-formylbenzoic acid, butylamine and diethyl phosphite was monitored by in situ FT-IR spectroscopy. The novel title compounds could be prepared in high yields at low temperature under a short reaction time. A suitable method could also be developed for the preparation of the isoindolin-1-one-3-phosphonates at a “few g” scale by using a continuous flow MW reactor. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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16 pages, 1641 KiB

Open AccessArticle

Synthesis and In Vitro Cytotoxicity and Antibacterial Activity of Novel 1,2,3-Triazol-5-yl-Phosphonates

by Anna Tripolszky, Emese Tóth, Pál Tamás Szabó, László Hackler, Jr., Beáta Kari, László G. Puskás and Erika Bálint

Molecules 2020, 25(11), 2643; https://doi.org/10.3390/molecules25112643 - 06 Jun 2020

Cited by 8 | Viewed by 2519

Abstract

Novel 1,2,3-triazol-5-yl-phosphonates were prepared by the copper(I)-catalyzed domino reaction of phenylacetylene, organic azides and dialkyl phosphites. The process was optimized on the synthesis of the dibutyl (1-benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)phosphonate in respect of the catalyst, the base and the solvent, as well as of [...] Read more.

Novel 1,2,3-triazol-5-yl-phosphonates were prepared by the copper(I)-catalyzed domino reaction of phenylacetylene, organic azides and dialkyl phosphites. The process was optimized on the synthesis of the dibutyl (1-benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)phosphonate in respect of the catalyst, the base and the solvent, as well as of the reaction parameters (molar ratio of the starting materials, atmosphere, temperature and reaction time). The method elaborated could be applied to a range of organic azides and dialkyl phosphites, which confirmed the large scope and the functional group tolerance. The in vitro cytotoxicity on different cell lines and the antibacterial activity of the synthesized 1,2,3-triazol-5-yl-phosphonates was explored. According to the IC₅₀ values determined, only modest antibacterial effect was detected, while some derivatives showed moderate activity against human promyelocytic leukemia HL-60 cells. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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14 pages, 3158 KiB

Open AccessArticle

The Synthesis of α-Aminophosphonates via Enantioselective Organocatalytic Reaction of 1-(N-Acylamino)alkylphosphonium Salts with Dimethyl Phosphite

by Alicja Walęcka-Kurczyk, Krzysztof Walczak, Anna Kuźnik, Sebastian Stecko and Agnieszka Październiok-Holewa

Molecules 2020, 25(2), 405; https://doi.org/10.3390/molecules25020405 - 18 Jan 2020

Cited by 11 | Viewed by 4026

Abstract

α-Aminophosphonic acids are phosphorus analogues of α-amino acids. Compounds of this type find numerous applications in medicine and crop protection due to their unique biological activities. A crucial factor in these activities is the configuration of the stereoisomers. Only a few methods of [...] Read more.

α-Aminophosphonic acids are phosphorus analogues of α-amino acids. Compounds of this type find numerous applications in medicine and crop protection due to their unique biological activities. A crucial factor in these activities is the configuration of the stereoisomers. Only a few methods of stereoselective transformation of α-amino acids into their phosphorus analogues are known so far and all of them are based on asymmetric induction, thus involving the use of a chiral substrate. In contrast, we have focused our efforts on the development of an effective method for this type of transformation using a racemic mixture of starting N-protected α-amino acids and a chiral catalyst. Herein, a simple and efficient stereoselective organocatalytic α-amidoalkylation of dimethyl phosphite by 1-(N-acylamino)alkyltriphenylphosphonium salts to enantiomerically enriched α-aminophosphonates is reported. Using 5 mol% of chiral quinine- or hydroquinine-derived quaternary ammonium salts provides final products in very good yields up to 98% and with up to 92% ee. The starting phosphonium salts were easily obtained from α-amino acid derivatives by decarboxylative methoxylation and subsequent substitution with triphenylphosphonium tetrafluoroborate. The appropriate self-disproportionation of enantiomers (SDE) test for selected α-aminophosphonate derivatives via achiral flash chromatography was performed to confirm the reliability of the enantioselectivity results that were obtained. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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10 pages, 1555 KiB

Open AccessArticle

Michaelis-Arbuzov-Type Reaction of 1-Imidoalkyltriarylphosphonium Salts with Selected Phosphorus Nucleophiles

by Jakub Adamek, Anna Węgrzyk-Schlieter, Klaudia Steć, Krzysztof Walczak and Karol Erfurt

Molecules 2019, 24(18), 3405; https://doi.org/10.3390/molecules24183405 - 19 Sep 2019

Cited by 5 | Viewed by 3001

Abstract

In this study, Michaelis-Arbuzov-type reaction of 1-imidoalkyltriarylphosphonium salts with phosphites, phosphonites, and phosphinites was used in the synthesis of a wide range of phosphorus analogs of α-amino acids such as 1-imidoalkylphosphonates, 1-imidoalkylphosphinates, and 1-imidoalkylphosphine oxides. Large differences were observed in the reactivity of [...] Read more.

In this study, Michaelis-Arbuzov-type reaction of 1-imidoalkyltriarylphosphonium salts with phosphites, phosphonites, and phosphinites was used in the synthesis of a wide range of phosphorus analogs of α-amino acids such as 1-imidoalkylphosphonates, 1-imidoalkylphosphinates, and 1-imidoalkylphosphine oxides. Large differences were observed in the reactivity of substrates depending on their structure, especially on the type of phosphonium moiety and N-protecting group. The conditions under which the expected products can be obtained in good to excellent yields have been developed. Mechanistic aspects of the transformation have been provided. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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15 pages, 3482 KiB

Open AccessArticle

Insight into the Synthesis and Characterization of Organophosphorus-Based Bridged Triazine Compounds

by Khalifah A. Salmeia, Antonia Neels, Dambarudhar Parida, Sandro Lehner, Daniel Rentsch and Sabyasachi Gaan

Molecules 2019, 24(14), 2672; https://doi.org/10.3390/molecules24142672 - 23 Jul 2019

Cited by 14 | Viewed by 4694

Abstract

In this article, we report the synthesis of 2,4,6-substituted s-triazine-based organophosphorus compounds via a two-step process, which enables their production in high yields, and with a high purity as solids. In the first step, a Michaelis–Arbuzov rearrangement of cyanuric chloride with triethyl [...] Read more.

In this article, we report the synthesis of 2,4,6-substituted s-triazine-based organophosphorus compounds via a two-step process, which enables their production in high yields, and with a high purity as solids. In the first step, a Michaelis–Arbuzov rearrangement of cyanuric chloride with triethyl phosphite afforded 2,4,6-trisdiethoxyphosphinyl-1,3,5-triazine (HEPT). Subsequently, the nucleophilic substitution reaction on the triazine carbon was achieved, owing to the electron-withdrawing ability of the phosphonate groups. This characteristic of HEPT facilitated its derivatization with bi-functional amines, producing novel P–C containing bridged triazine organophosphorus compounds. The molecular structures of all of the compounds were confirmed by NMR spectroscopy, CHN elemental analysis, and single crystal X-ray analysis. In the thermogravimetric analysis in an N₂ environment, >33% char formation was observed for the bridged compounds. The chemical composition analysis of the char obtained under the oxidative thermal decomposition of the bridged compounds confirmed the presence of phosphorus- and nitrogen-enriched species, which indicate their function in the condensed phase. Comparatively, the detection of HPO and H–C≡P in the gas phase during the pyrolysis of the bridged compounds can act as a source for PO^•, which is known for its gas phase flame inhibition reactions. The synergy of significant char formation and the generation of intermediates leading to PO^• during pyrolysis makes these molecules promising flame-retardant additives. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Utilization of Organophosphorus Compounds)

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