Progress in Synthesis and Applications of Phosphorus-Containing Compounds

A special issue of Organics (ISSN 2673-401X).

Deadline for manuscript submissions: closed (30 November 2022) | Viewed by 23512

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Guest Editor
Department of Physical and Quantum Chemistry, Faculty of Chemistry, Wroclaw University of Science and Technology, Wybrzeze Wyspianskiego 29, 50-370 Wroclaw, Poland
Interests: catalysis; olefin metathesis; NHC complexes; chemistry of hetero-organic compounds; carbohydrate chemistry; asymmetric synthesis; green chemistry
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Special Issue Information

Dear Colleagues,

Organophosphorus compounds, due to their interesting physicochemical properties, have found wide applications in many important areas of the chemical industry, such as the synthesis of utility chemicals (e.g., flame retardants, anticorrosive coatings, and adhesives), ligands for catalysis, agrochemicals (e.g., insecticides, herbicides, and fungicides), and, finally, pharmaceutically active compounds. Unsurprisingly, owing to the importance of phosphorus-containing compounds, several methods have emerged for their effective synthesis also in an asymmetric fashion.

This Special Issue of Organics aims to provide an overview of the latest progress in the Synthesis and Applications of Phosphorus-Containing Compounds. Experimental contributions, including full papers, communications, as well as reviews describing the synthesis and applications of organophosphorus compounds are welcome.

As a Guest Editor, it is my pleasure to invite all researchers working in the exciting and wide field of organophosphorus chemistry to contribute to this inaugural Special Issue of Organics. Importantly, this personal invitation entitles authors to publish their high-quality contributions free of charge.

Dr. Tomasz K. Olszewski
Guest Editor

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Keywords

  • Phosphorus
  • Phosphonates
  • Phosphines
  • Phosphonic acids
  • Phosphinic acids
  • Phosphine oxides
  • Catalysis
  • Asymmetric synthesis
  • Biologically active compounds
  • Agrochemicals
  • Anticorrosive coatings and adhesives
  • Flame retardants
  • Polymers

Published Papers (10 papers)

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Research

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17 pages, 2780 KiB  
Article
Triple Benefits of Cardanol as Chain Stopper, Flame Retardant and Reactive Diluent for Greener Alkyd Coating
by Maxinne Denis, Cédric Totée, Damien Le Borgne, Rodolphe Sonnier, Sylvain Caillol and Claire Negrell
Organics 2023, 4(1), 109-125; https://doi.org/10.3390/org4010009 - 15 Mar 2023
Cited by 2 | Viewed by 1852
Abstract
Cardanol, a waste from the food industry and widely produced (1 Mt/y), has been used as a chain stopper during the polycondensation of short oil alkyd resins in order to replace benzoic acid. Then, phosphorylated cardanol has been added in order to both [...] Read more.
Cardanol, a waste from the food industry and widely produced (1 Mt/y), has been used as a chain stopper during the polycondensation of short oil alkyd resins in order to replace benzoic acid. Then, phosphorylated cardanol has been added in order to both reduce solvent content and bring flame-retardant (FR) properties to the alkyd resins. The renewable carbon content of the formulations has been increased up to 23%. The impact of the introduction of phosphorylated cardanol molecules on the drying time and flexibility has been studied as well as the thermal and flame-retardant properties by differential scanning calorimeter, thermogravimetric analysis and pyrolysis-combustion flow calorimeter. The most effective flame-retardant coating that was associated with excellent FR properties and excellent coating properties has been obtained with phosphate-cardanol added at 2%wt of P. Indeed, the film properties were closed to the classical alkyd resin, the solvent content was reduced by 50% and the pHRR decreased by 42% compared to the reference alkyd resin. Full article
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11 pages, 1031 KiB  
Article
Synthesis and Wittig Rearrangement of 3- and 4-Benzyloxyphenylphosphonamidates
by R. Alan Aitken and Ryan A. Inwood
Organics 2023, 4(1), 59-69; https://doi.org/10.3390/org4010005 - 3 Feb 2023
Cited by 2 | Viewed by 1455
Abstract
A series of seven O-ethyl-N-butylphenylphosphonamidates with benzyl ether substituents at the para or meta position have been prepared and fully characterised. Upon treatment with n-butyllithium in THF at RT, these undergo Wittig rearrangement in six cases to give the [...] Read more.
A series of seven O-ethyl-N-butylphenylphosphonamidates with benzyl ether substituents at the para or meta position have been prepared and fully characterised. Upon treatment with n-butyllithium in THF at RT, these undergo Wittig rearrangement in six cases to give the novel phosphonamidate-substituted diarylmethanols in moderate to good yield. Full article
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11 pages, 1564 KiB  
Article
How Do Positions of Phosphito Units on a Calix[4]Arene Platform Affect the Enantioselectivity of a Catalytic Reaction?
by Shaima Hkiri and David Sémeril
Organics 2022, 3(4), 470-480; https://doi.org/10.3390/org3040030 - 9 Nov 2022
Cited by 1 | Viewed by 1403
Abstract
Three chiral diphosphites, (S,S)-5,17-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)-25,26,27,28-tetrapropyloxycalix[4]arene (1), (S,S)-5,11,17,23-tetra-tert-butyl-25,27-dipropoxy-26,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (2) and (S,S)-5,11,17,23-tetra-tert-butyl-25,26-dipropoxy-27,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (3), based on conical calix[4]arene were investigated in the rhodium-catalyzed asymmetric hydrogenation [...] Read more.
Three chiral diphosphites, (S,S)-5,17-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)-25,26,27,28-tetrapropyloxycalix[4]arene (1), (S,S)-5,11,17,23-tetra-tert-butyl-25,27-dipropoxy-26,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (2) and (S,S)-5,11,17,23-tetra-tert-butyl-25,26-dipropoxy-27,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (3), based on conical calix[4]arene were investigated in the rhodium-catalyzed asymmetric hydrogenation of α-dehydroamino esters. High conversions were observed after 24 h under 5 bar of hydrogen whatever the employed diphosphite, and the chiral induction increases in the order 1 < 3 < 2. This may be due to the presence of the calix[4]arene moiety, which by its presence modifies the second coordination sphere of the catalytic center. The larger steric hindrance around the rhodium atom leads to the higher enantiomeric excess. Full article
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12 pages, 686 KiB  
Article
Regioselective N- versus P-Deprotonation of Aminophosphane Tungsten(0) Complexes
by Tatjana Terschüren, Philip Junker, Alexander Schmer, Arturo Espinosa Ferao and Rainer Streubel
Organics 2022, 3(3), 161-172; https://doi.org/10.3390/org3030013 - 22 Jun 2022
Viewed by 1720
Abstract
1,2-Bifunctional ligands are rare, in general, which holds especially for those with a P-N linkage. Herein, we report on the synthesis of P-tert-butyl substituted aminophosphane W(CO)5 complexes 3a-f (a: R = R’ = H; b: R = H, R = Me; [...] Read more.
1,2-Bifunctional ligands are rare, in general, which holds especially for those with a P-N linkage. Herein, we report on the synthesis of P-tert-butyl substituted aminophosphane W(CO)5 complexes 3a-f (a: R = R’ = H; b: R = H, R = Me; c: R = H, R’ = ally; d: R = H, R’ = i-Pr; e: R = H, R’ = t-Bu; f: R = R’ = Me) obtained via formal N-H insertion reactions of Li/Cl phosphinidenoid complex 2 into NH bonds of ammonia and different amines. The 1,2-bifunctionality of 3b was addressed in targeted regioselective deprotonation reactions leading to amidophosphane complexes M-4b or M/N(H)Me phosphinidenoid complexes M-5b, respectively (M = Li, K). Remarkable was the observation that reactions of M-4b and M-5b with MeI as the electrophile resulted in the formation of the same product 7b. The constitution of all the compounds has been established by means of NMR and IR spectroscopy and mass spectrometry. Two possible reaction pathways were studied in detail using high-level DFT calculations. Full article
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9 pages, 10073 KiB  
Article
Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes
by Toshiaki Murai, Ryota Wada, Kouji Iwata, Yuuki Maekawa, Kazuma Kuwabara and Mao Minoura
Organics 2021, 2(4), 395-403; https://doi.org/10.3390/org2040023 - 16 Nov 2021
Cited by 4 | Viewed by 2872
Abstract
Organophosphorus compounds with stereogenic phosphorus and carbon atoms have received increasing attention. In this regards, primary phosphines with a stereogenic carbon atom adjacent to the phosphorus atom were synthesized by the reduction in phosphonates and phosphonoselenoates with a binaphthyl group. Their oxidized products, [...] Read more.
Organophosphorus compounds with stereogenic phosphorus and carbon atoms have received increasing attention. In this regards, primary phosphines with a stereogenic carbon atom adjacent to the phosphorus atom were synthesized by the reduction in phosphonates and phosphonoselenoates with a binaphthyl group. Their oxidized products, i.e., phosphine oxides with a stereogenic tetrasubstituted carbon atom, were found to undergo BEt3-mediated radical addition to cyclohexene to give P-stereogenic secondary phosphine oxides with a diastereoselectivity of 91:9. The products were characterized by ordinary analytical methods, such as Fourier transform infrared spectroscopy; 1H, 13C, and 31P NMR spectroscopies; and mass spectroscopy. Computational studies on the phosphorus-centered radical species and the obtained product implied that the thermodynamically stable radical and the adduct may be formed as a major diastereomer. The radical addition to a range of alkenes took place in an anti-Markovnikov fashion to give P-stereogenic secondary phosphine oxides. A variety of functional groups in the alkenes were tolerated under the reaction conditions to afford secondary phosphine oxides in moderate yields. Primary phosphines with an alkenyl group, which were generated in situ, underwent intramolecular cyclization to give five- and six-membered cyclic phosphines in high yields after protection by BH3. Full article
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9 pages, 3720 KiB  
Article
MCR under Microwave Irradiation: Synthesis in Water of New 2-Amino-bis(2-phosphonoacetic) Acids
by Didier Villemin, Bernard Moreau and Nathalie Bar
Organics 2021, 2(2), 98-106; https://doi.org/10.3390/org2020009 - 11 May 2021
Cited by 2 | Viewed by 3007
Abstract
Novel 2-amino bis(2-phosphonoacetic) acids were prepared by microwave irradiation of a mixture of amine, glyoxylic acid and phosphorous acid. The reaction takes place with various amines including primary and secondary amines and polyamines, but this reaction is more sensitive to steric hindrance of [...] Read more.
Novel 2-amino bis(2-phosphonoacetic) acids were prepared by microwave irradiation of a mixture of amine, glyoxylic acid and phosphorous acid. The reaction takes place with various amines including primary and secondary amines and polyamines, but this reaction is more sensitive to steric hindrance of amine than the similar Kabachnik–Fields reaction. Amino acids can be also transformed into the expected bis(2-phosphonoacetic) acids, with the exception of tryptophan, which gives a β-carboline product. Full article
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14 pages, 6647 KiB  
Article
Z,E-Isomerism in a Series of Substituted Iminophosphonates: Quantum Chemical Research
by Alexander B. Rozhenko, Andrey A. Kyrylchuk, Yuliia O. Lapinska, Yuliya V. Rassukana, Vladimir V. Trachevsky, Volodymyr V. Pirozhenko, Jerzy Leszczynski and Petro P. Onysko
Organics 2021, 2(2), 84-97; https://doi.org/10.3390/org2020008 - 23 Apr 2021
Cited by 3 | Viewed by 3555
Abstract
Esters of iminophosphonic acids (iminophosphonates, or IPs), including a fragment, >P(=O)-C=N, can be easily functionalized, for instance to aminophosphonic acids with a wide range of biological activity. Depending on the character of the substitution, the Z- or E-configuration is favorable for IPs, which [...] Read more.
Esters of iminophosphonic acids (iminophosphonates, or IPs), including a fragment, >P(=O)-C=N, can be easily functionalized, for instance to aminophosphonic acids with a wide range of biological activity. Depending on the character of the substitution, the Z- or E-configuration is favorable for IPs, which in turn can influence the stereochemistry of the products of chemical transformations of IPs. While the Z,E-isomerism in IPs has been thoroughly studied by NMR spectroscopy, the factors stabilizing a definite isomer are still not clear. In the current work, density functional theory (DFT, using M06-2X functional) and ab initio spin-component–scaled second-order Møller–Plesset perturbation theory (SCS-MP2) calculations were carried out for a broad series of IPs. The calculations reproduce well a subtle balance between the preferred Z-configuration inherent for C-trifluoromethyl substituted IPs and the E-form, which is more stable for C-alkyl- or aryl-substituted IPs. The predicted trend of changing activation energy values agrees well with the recently determined experimental ΔG298 magnitudes. Depending on the substitution in the aromatic moiety, the Z/E-isomerization of N-aryl-substituted IPs proceeds via two types of close-in energy transition states. Not a single main factor but a combination of various contributions should be considered in order to explain the Z/E-isomerization equilibrium for different IPs. Full article
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12 pages, 1235 KiB  
Article
α-(Imino)pyridyldifluoroethyl Phosphonates: Novel Promising Building Blocks in Synthesis of Biorelevant Aminophosphonic Acids Derivatives
by Oksana M. Shavrina, Lyudmyla V. Bezgubenko, Andrii V. Bezdudny, Petro P. Onys’ko and Yuliya V. Rassukana
Organics 2021, 2(2), 72-83; https://doi.org/10.3390/org2020007 - 23 Apr 2021
Cited by 1 | Viewed by 2800
Abstract
A convenient synthetic approach to previously unknown NH-iminophosphonates bearing 2-, 3-, and 4-pyridyldifluoromethyl groups at the imine carbon atom was developed. The synthetic potential of these novel building blocks was demonstrated by their conversion into highly functionalized acyclic and heterocyclic aminophosphonates and phosphonic [...] Read more.
A convenient synthetic approach to previously unknown NH-iminophosphonates bearing 2-, 3-, and 4-pyridyldifluoromethyl groups at the imine carbon atom was developed. The synthetic potential of these novel building blocks was demonstrated by their conversion into highly functionalized acyclic and heterocyclic aminophosphonates and phosphonic acids combining in their structure biorelevant aminophosphonic fragment, difluoromethyl group, and pyridyl, piperidyl, thiazolidin-4-one, or thiazidinan-4-one heterocyclic moieties in a single molecular platform. Full article
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Review

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17 pages, 2912 KiB  
Review
An Overview of Some Reactive Routes to Flame-Retardant Fibre-Forming Polymers: Polypropylene and Polyacrylonitrile
by Svetlana Tretsiakova-McNally, Malavika Arun, Maurice Guerrieri and Paul Joseph
Organics 2023, 4(3), 386-402; https://doi.org/10.3390/org4030028 - 12 Jul 2023
Viewed by 1122
Abstract
The thermal degradation and flammability characteristics of some common fibre-forming polymers, such as polypropylene (PP) and polyacrylonitrile (PAN), are described in this review paper. The flame retardance of these polymers is principally affected by reactive routes that were primarily developed in our laboratories. [...] Read more.
The thermal degradation and flammability characteristics of some common fibre-forming polymers, such as polypropylene (PP) and polyacrylonitrile (PAN), are described in this review paper. The flame retardance of these polymers is principally affected by reactive routes that were primarily developed in our laboratories. The modifying groups that are incorporated into polymeric chains include phosphorus- or phosphorus/nitrogen-containing moieties in different chemical environments. The degradation characteristics and extent of flame retardance were mainly evaluated using routine thermal and calorimetric techniques. Elements of flame-retardant mechanisms occurring in the condensed and vapour phases were also identified. Furthermore, we also explored the effects of molecularly dispersed β-cyclodextrin, including its physical mixtures, on the thermal and combustion characteristics of PAN. Given that both types of polymers are often used in the form of fibres, and that the aspect ratio of fibrous materials is relatively high, even nominal enhancements in their fire retardance are highly welcomed. Hence, the preliminary results of our research on chemically modified PAN incorporating molecularly dispersed β-cyclodextrin are encouraging in terms of their enhanced fire retardance, and hence this field warrants further exploration. Full article
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22 pages, 9369 KiB  
Review
Specific Bifunctionalization on the Surface of Phosphorus Dendrimers Syntheses and Properties
by Massimo Petriccone, Régis Laurent, Cédric-Olivier Turrin, Rosa Maria Sebastián and Anne-Marie Caminade
Organics 2022, 3(3), 240-261; https://doi.org/10.3390/org3030018 - 3 Aug 2022
Cited by 2 | Viewed by 2072
Abstract
Dendrimers are highly branched macromolecules possessing, in most cases, identical terminal functions. However, it is sometimes desirable to have two types of surface functions in order to fulfil specific properties. The stochastic functionalization is frequently used for such purposes, but the presence of [...] Read more.
Dendrimers are highly branched macromolecules possessing, in most cases, identical terminal functions. However, it is sometimes desirable to have two types of surface functions in order to fulfil specific properties. The stochastic functionalization is frequently used for such purposes, but the presence of an uncontrolled number of each type of terminal function, albeit acceptable for research purposes, has no practical use. Thus, it is highly desirable to find strategies suitable for the precise grafting of two different functional groups on the surface of dendrimers. The easiest way, and the most widely used, consists in using a bifunctional monomer to be grafted to all of the surface functions of the dendrimers. Two other strategies are known but are rarely used: the modification of an existing function, to generate two functions, and the sequential grafting of one function then of a second function. The three methods are illustrated in this review with polyphosphorhydrazone (PPH) dendrimers, together with their properties as catalysts, for materials, and as biological tools. Full article
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