Oxidation of white phosphorus by peroxides in aqueous and alcoholic solutions: mechanistic aspects and catalytic studies

Akbayeva, Dina N.; Faisova, Farida Kh.; Abdreimova, R. R.; Peruzzini, Maurizio

doi:10.1016/j.molcata.2006.11.046

Cited by 14 publications

(15 citation statements)

References 62 publications

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“…In comparison, direct oxidation of P4 using peroxide reagents is known to be much less selective. 56 HPA is another important P1 precursor, used to prepare phosphinic acid derivatives (e.g. Cyanex ® , used in metal separation processes), 9 and is also employed industrially as a reductant (e.g.…”

Section: Functionalisation Of (Bu3sn)xph3-xmentioning

confidence: 99%

“…10% HP(O)(OH)2 (as judged by 31 P{ 1 H} NMR spectroscopy), which is a known oxidation product of H2P(O)OH. 56 In order to ascertain the H2O content, quantitative 31 P{ 1 H} NMR spectroscopic analysis (D1 = 14 s) was performed on a CD3CN solution containing precisely known quantities of both this product (6.5 mg) and Ph3PO (23.0 mg), with the latter acting as an internal standard for integration. In this manner the precise amount of HPA (and HP(O)(OH)2) in the sample could be calculated, with the remaining mass being attributed to H2O.…”

Section: Synthesis and Isolation Of Hpa (19) With Recovery Of Bu3sncl (20)mentioning

confidence: 99%

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Synthesis of monophosphines directly from white phosphorus

et al. 2021

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Monophosphorus compounds are of enormous industrial importance due to the crucial roles they play in applications including pharmaceuticals, photoinitiators, and ligands for catalysis, among many others. White phosphorus (P4) is the key starting material for the preparation of all such chemicals. However, current production depends upon indirect and inefficient, multistep procedures. Here, we report a simple, effective 'one pot' synthesis of a wide range of organic and inorganic monophosphorus species directly from P4. Reduction of P4 using tri-nbutyltin hydride and subsequent treatment with various electrophiles affords compounds that are of key importance for the chemical industry, and requires only mild conditions and inexpensive, easily handled reagents. Crucially, we also demonstrate facile and efficient recycling and ultimately even catalytic use of the tributyltin reagent, thereby avoiding the formation of significant Sn-containing waste. Accessible, industrially relevant products include the fumigant PH3, the reducing agent hypophosphorous acid, and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride. Main TextWhite phosphorus (P4) is one of the most important synthetic feedstocks for the modern chemical industry, 1 and is produced on a scale of > 1 Mt per year. The pyrophoric nature of P4 and its hazardous and energy-intensive synthesis from phosphate ores have prompted recent academic efforts to bypass this compound and instead use phosphate materials directly as synthetic precursors. [2][3][4] Other researchers have emphasized the need to develop more sustainable routes for the recycling and reuse of P-containing materials, which are otherwise 2 lost as environmentally-hazardous wastes. 2,5,6 However, despite these efforts, P4 remains the only industrially-viable precursor from which to prepare the vast majority of monophosphorus compounds, which find applications ranging from pharmaceuticals to chemical catalysts. [7][8][9] Unfortunately, state-of-the-art industrial methods for the synthesis of these useful P1 species rely on indirect and correspondingly inefficient multi-step processes. The most common route (Fig. 1a) involves oxidation of P4 by toxic Cl2 gas to generate extremely corrosive PCl3. 10 Treatment with suitable nucleophiles then provides the desired products via substitution of chloride, with concomitant generation of chloride-containing waste. Alternatively, some P1 products can be generated by hydrophosphination of unsaturated organic compounds using PH3 gas. However, industrial-scale preparation of PH3 involves acid-catalysed or alkalimediated disproportionation of P4, which demands harsh reactions conditions and produces phosphorus oxyacid derivatives as stoichiometric byproducts (Figure 1). 10 Recognition of the deficiencies of current routes for generating P1 products has prompted a strong desire to discover reactions that are capable of transforming P4 into these useful compounds directly, bypassing the need for isolation and manipulation of potentially hazard...

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Section: Functionalisation Of (Bu3sn)xph3-xmentioning

confidence: 99%

Section: Synthesis and Isolation Of Hpa (19) With Recovery Of Bu3sncl (20)mentioning

confidence: 99%

Synthesis of monophosphines directly from white phosphorus

et al. 2021

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“…The electrochemical oxidation of white phosphorus has received much less attention owing to the ease of chemical oxidation of P 4 in the gas phase by molecular oxygen or in aqueous solutions,51 thereby resulting in the formation of different oxyacids. The phosphoric H 3 PO 4 and phosphorus H 3 PO 3 acids can be selectively obtained in neutral and acidic media by an anodic electrochemical process during electrolysis on porous conductive matrices 52.…”

Section: Electrode Reactions Of Elemental (White) Phosphorusmentioning

confidence: 99%

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

2013

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Electrochemical methods have become important from the viewpoint of the development and creation of new ecologically safe and resource‐saving chemical processes. The use of electrons as a “universal” and “inexhaustible” reagent for chemical reactions is the main advantage of electrochemical tools. Although electrochemical processes have been already successfully applied in the preparation of different classes of practically important chemical compounds, a very limited number of industrially applicable electrochemical processes that involve elemental (white) phosphorus is currently known, except for some examples of the electrochemical production of phosphane PH3. These are mainly associated with the investigation of bulk reactions of the electrochemically activated P4 molecule and phosphorus intermediates derived therefrom; very limited attention has been paid to the electrode surface reactions as a key stage of the electrochemical process. In this Microreview we describe the electrode reactions of elemental (white) phosphorus and phosphane that accompany the electrochemical process of the preparation of some phosphorus compounds starting directly from P4. The important role of the nature of the electrode material, the reactivity of the formed phosphorus intermediates and the surface processes are discussed. Moreover, recently, we succeeded in discovering a new, previously unstable phosphorus compound, phosphane oxide H3PO, which can be easily produced using an electrochemical method by mild anodic oxidation of phosphane PH3 electrochemically formed from P4. In this respect, some attention has been paid to the electrochemically induced processes of PH3 oxidation that result in the selective formation of phosphane oxide, which is of high interest from the viewpoint of the investigation of its properties and reactivity.

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“…In the past several decades, the catalytic method for the synthesis of OPCs from P 4 has rarely been reported, and only four methods for the direct preparation of triaryl phosphates from P 4 have been developed (Scheme ). Compared to R alkyl O – anions, ArO – anions are difficult to react with P 4 because of the low nucleophilicity in solution . Attempts to construct P–OAr bonds by using CCl 4 as the electrophilic component were made by Ivanov and co-workers with an excess of crown ether to increase the actual concentration of ArO – anions in CCl 4 (Scheme A) .…”

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Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus

et al. 2021

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Industrially important triaryl phosphites, traditionally prepared from PCl 3 , have been synthesized by a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen-and transition metalfree way to these compounds. Subsequent oxidation of triaryl phosphites produces triaryl phosphates and triaryl thiophosphates. Phosphorotrithioates are also prepared efficiently from aromatic thiols and aliphatic thiols.

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Oxidation of white phosphorus by peroxides in aqueous and alcoholic solutions: mechanistic aspects and catalytic studies

Cited by 14 publications

References 62 publications

Synthesis of monophosphines directly from white phosphorus

Synthesis of monophosphines directly from white phosphorus

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus

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Oxidation of white phosphorus by peroxides in aqueous and alcoholic solutions: mechanistic aspects and catalytic studies

Cited by 14 publications

References 62 publications

Synthesis of monophosphines directly from white phosphorus

Synthesis of monophosphines directly from white phosphorus

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH3

Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus

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Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃