Elemental Phosphorus in the Synthesis of Organophosphorus Compounds: The Recent Advances (A Review) (original) (raw)
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Single-stage synthesis of alkyl-H-phosphinic acids from elemental phosphorus and alkyl bromides
Mendeleev Communications, 2019
Organic H-phosphinic acids, RPH(O)(OH), are now widely explored and applied as prospective ligands for metal complex catalysts inducing many types of transformations, 1 drug precursors, 2 reagents for hydrometallurgy, 3 retardants, 4 surfactants 5 and building blocks for the preparation of in-demand phosphinic, 6 phosphonic 7 acids or other valuable compounds. 8 Therefore, search for the methods of convenient synthesis of organic H-phospinic acids is topical. 9 The tradi tional syntheses of these compounds are based on hydrolysis of harmful, aggressive and expensive alkyl-or aryl dichlorophos phines. 10 In recent years, the methods for synthesis of phosphinic acids by the reactions of hypophosphorous acid, H 3 PO 2 (prepared from white phosphorus 10), with alkenes, 3,11 alkynes, 11(b) and alkyl halides 11(a),(c) were intensively developing. Usually, these reactions proceed in the presence of Pd catalysts, 11(a)-(c),12 under microwave activation 6(d) or radical conditions. 3,13 Here, we report on a facile one-pot synthesis of alkyl-Hphosphinic acids by the direct phosphorylation of alkyl bromides with elemental phosphorus in the presence of strong bases. Previously, we have shown 14 that alkyl bromides react with red phosphorus (P n) in the KOH/H 2 O/THF (or dioxane) system (the RBr : P n : KOH ratio was 1 : 1.25 : 5) at 60-65 °C in the presence of triethylbenzylammonium chloride as the phase-transfer catalyst. The main products turned to be tertiary trialkylphosphine oxides Alk 3 P(O) (41-69% yields) while the yields of the corresponding practically useful 15 secondary dialkylphosphine oxides Alk 2 P(O)H did not exceed 4%. The formation of alkyl-H-phosphinic acids under these conditions did not occur. After several experiments with red (P n) or white (P 4) phosphorus and n-hexyl bromide 1a (Scheme 1, Table 1, entries 1-6), synthetically reasonable conditions for the preparation of n-hexyl-H-phosphinic acid 2a in 41-47% yield with good conver sion
ACS Central Science, 2021
Phosphorus-based organocatalysis encompasses several subfields that have undergone rapid growth in recent years. This Outlook gives an overview of its various aspects. In particular, we highlight key advances in three topics: nucleophilic phosphine catalysis, organophosphorus catalysis to bypass phosphine oxide waste, and organophosphorus compound-mediated single electron transfer processes. We briefly summarize five additional topics: chiral phosphoric acid catalysis, phosphine oxide Lewis base catalysis, iminophosphorane super base catalysis, phosphonium salt phase transfer catalysis, and frustrated Lewis pair catalysis. Although it is not catalytic in nature, we also discuss novel discoveries that are emerging in phosphorus(V) ligand coupling. We conclude with some ideas about the future of organophosphorus catalysis.
Environmentally Friendly Chemistry with Organophosphorus Syntheses in Focus
Periodica Polytechnica Chemical Engineering, 2015
The use of the microwave (MW) technique has many advan tages in organophosphorus chemistry. MW irradiation may replace a catalyst, or simplify a catalytic system. New reactions may also become possible under MW irradiation. In most cases, microwaves just make the reactions more efficient in respect of rate, selectivity and yield. The benefits are shown via representative examples. In another field, our methods developed for the resolution of cyclic phosphine oxides and phosphinates are summarized. After deoxygenation, the racemic or optically active Pheterocycles were used as Pligands in platinum complexes that together with other derivatives are potential catalysts. The third topic embraces the optimization of the synthesis of dronic acids/dronates. Starting from the cor responding carboxylic acids and using methanesulfonic acid as the solvent, 3 equivalents of phosphorus trichloride is enough as the Preactant. Applying sulfolane as the solvent, the opti mum set of reactants comprises 2 equivalents of phosphorus trichloride and phosphorous acid.
Synthesis of organophosphates starting from α-hydroxyphosphonates
Phosphorus, Sulfur, and Silicon and the Related Elements, 2018
a-Hydroxyphosphonates were successfully converted to the corresponding phosphates applying the phospha-Brook rearrangement under phase transfer catalytic conditions. Among several possible catalysts tested, K 2 CO 3 , Cs 2 CO 3 , as well as modified Moroccan phosphates were found to be suitable.
Journal of the Chemical Society, Perkin Transactions 1, 1973
Novel polyphosphines can be prepared by the base-catalysed addition of R, P-H across the carbon-carbon double bonds of vinylphosphonate esters, followed by reduction with lithium aluminium hydride. Thus a tertiary-primary diphosphine, a tertiary-diprimary triphosphine, a tertiary-triprimary tripod tetraphosphine, and a ditertiary-diprimary linear tetraphosphine have been prepared. Similarly, the tertiary-secondary diphosphine Ph,P*CH,-CH,*PH Ph can be prepared by base-catalysed addition of diphenylphosphine to isopropyl phenylvinylphosphinate followed by reduction. The secondary-primary diphosphine PhPH*CH,*CH,*PH, can be prepared by the Arbusov reaction of di-isopropoxy(pheny1)phosphine with di-isopropyl 2-bromoethylphosphonate followed by reduction. The i.r., l H n.m.r., sl P n.m.r.. and mass spectra of the new compounds are discussed.
Materials
In order to obtain sulfur-containing organophosphorus compounds that are promising as extractants of heavy metals, the interaction of elemental phosphorus and sulfur with alkyl bromides catalyzed using strong bases was studied. According to the task, the reaction of non-toxic and non-flammable red phosphorus with alkyl bromides under conditions of phase transfer catalysts (PTC), followed by the introduction of elemental sulfur into the reaction medium, were studied. It is shown that alkyl bromides interact with red phosphorus when heated (95–105 °C, 5–8 h) under conditions of phase transfer catalysts (PTC) in a two-phase system: a 60% aqueous solution of KOH-toluene-benzyltriethylammonium chloride (BTEAC) forming a mixture of organophosphorus compounds along with alkylphosphines (57–60%), are the main reaction products; alkylphosphine oxides are also formed (40–43%). The introduction of elemental sulfur (solution in toluene) at the final stage of the process into the reaction mass c...
Catalytic Synthesis of Phosphines and Related Compounds
Current Organic Chemistry, 2003
Abstract: Phosphines play an important role in organometallic chemistry, homogeneous catalysis and synthetic chemistry. Traditionally, phosphines are mainly prepared by one of the following methods: reaction of halophosphines with organometallic reagents, reaction ...
Recent developments in the chemistry of low-coordinated organophosphorus compounds
Pure and Applied Chemistry, 2005
Sterically protected organophosphorus compounds are described, involving diphosphenes, phosphaethenes, diphosphinidenecyclobutenes (DPCBs), phosphaalkynes, phosphaquinones, diphosphathienoquinones, and so on of coordination number 2 or 1. Application of the DPCBs as well as phosphinophosphaethenes as a ligand of transition-metal catalysts for several organic coupling reactions has been investigated.
Rapid and Efficient Synthesis ofω-Alkylenediphosphoric Acids from Phosphorus Oxychloride
Journal of Chemistry, 2016
The aim of this investigation was to develop an efficient, rapid, and selective method for the synthesis ofω-alkylenediphosphoric acids (HO)2(O)P-O-CH2n-O-P(O)(OH)2from reaction of several diols with phosphorus oxychloride. The reaction was investigated using three methodologies: (i) presence of a base, (ii) classical heating, and (iii) use of microwave irradiation. Influence of reaction temperature and molar ratio of reagents, as well as the nature of the solvent, was studied using these three different methods.