Triorganylphosphine oxides as high-performance fire retardants for polyvinyl chloride plastisols

Plotnikova, G. V.; Малышева, С. Ф.; Гусарова, Н. К.; Khalliulin, A. K.; Udilov, V. P.; Kuznetsov, Konstantin

doi:10.1134/s1070427208020286

Cited by 15 publications

(5 citation statements)

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“…Air-free handling is thus avoided until the final step, reduction − to a phosphine. It is worth noting that phosphine oxides are in and of themselves useful as biologically active molecules, as novel materials, , and as ligands in coordination chemistry. , …”

Section: Introductionmentioning

confidence: 99%

“…Air-free handling is thus avoided until the final step, reduction 16−21 to a phosphine. It is worth noting that phosphine oxides are in and of themselves useful as biologically active molecules, 22 as novel materials, 23,24 and as ligands in coordination chemistry. 25,26 We began by studying the reaction of secondary phosphine oxides (SPOs) with alkyl halide electrophiles to form a P−C bond (yielding tertiary phosphine oxides), which is currently a poorly developed area of chemistry.…”

Section: ■ Introductionmentioning

confidence: 99%

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Improved Synthetic Route to Heteroleptic Alkylphosphine Oxides

2017

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A new method for the synthesis of heteroleptic alkylphosphine oxides (R 2 R 1 PO, where R ≠ R 1 ) from secondary phosphine oxides (or SPOs, R 2 HPO) is presented. These reactions were fast at room temperature, sterically selective, high yielding, and >95% pure after an aqueous wash. Deprotonation of an SPO generates a phosphinite anion ([R 2 P− O] − ) that was found to be highly selective for nucleophilic P−C bond formation (as opposed to O−C bond formation) with alkyl halides. Surprisingly, most strong organometallic bases failed to deprotonate SPOs to their respective phosphinite anions (pK a s for most SPOs are <27). Only sodium bis(trimethylsilyl)amide (NaHMDS) cleanly formed the phosphinite anion, which was stable in solution (0.1 M, 23 °C in THF) for over 24 h. The need for a very specific base to deprotonate suggests that both ion pairing and the conjugate acid play a role in stabilizing the phosphinite anion. Phosphinite anion reactivity followed the expected trend for an S N 2 mechanism on reaction with alkyl halides; elimination products were never observed. A wide variety of heteroleptic alkylphosphine oxides were isolated in near-quantitative yield with only an aqueous wash as purification. This methodology was then used to make new bis(phosphine oxide)alkanes and unsymmetrical α,ω-bis(phosphine oxide)alkanes (R 2 P(O)(CH 2 ) 3 P(O)R 12 ) on the benchtop with unprecedented ease.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Improved Synthetic Route to Heteroleptic Alkylphosphine Oxides

2017

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“…Phosphines with 2-pyridyl substituents are used as CO-prodrugs in the treatment of leukemia [ 21 ]. Complexes of tris[2-(2-pyridyl)ethyl]phosphine chalcogenides are promising as precursors for the production of metal phosphides and selenides nanoparticles [ 30 ], and a complex of the phosphine oxide is used as a flame retardant for polymeric materials [ 31 ]. Considerable attention is devoted to the study of the coordination and donor properties of such polydentate ligands [ 32 , 33 , 34 , 35 , 36 ].…”

Section: Introductionmentioning

confidence: 99%

Structure of Tris[2-(4-pyridyl)ethyl]phosphine, Tris[2-(2-pyridyl)ethyl]phosphine, and Their Chalcogenides in Solution: Dipole Moments, IR Spectroscopy, and DFT Study

Kuznetsova,

Chachkov,

Belogorlova

et al. 2023

Molecules

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Tris(hetaryl)substituted phosphines and their chalcogenides are promising polydentate ligands for the design of metal complexes. An experimental and theoretical conformational analysis of tris[2-(4-pyridyl)ethyl]phosphine, tris[2-(2-pyridyl)ethyl]phosphine, and their chalcogenides was carried out by the methods of dipole moments, IR spectroscopy and DFT B3PW91/6-311++G(df,p) calculations. In solution, these compounds exist as an equilibrium of mainly non-eclipsed (synclinal or antiperiplanar) forms with a predominance of a symmetrical conformer having a gauche-orientation of the Csp3–Csp3 bonds of pyridylethyl substituents relative to the P=X bond (X = lone pair, O, S, Se) and a gauche-orientation of the pyridyl rings relative to the zigzag ethylene bridges. Regardless of the presence and nature of the chalcogen atom (oxygen, sulfur, or selenium) in the studied molecules with many axes of internal rotation, steric factors—the different position of the nitrogen atoms in the pyridyl rings and the configuration of ethylene bridges—determine the realization and spatial structure of preferred conformers.

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“…They are widely used as ligands for metal complex catalysts [1][2][3], special solvents for stabilization of nanosystems in the synthesis of semiconductors [4], extractants for noble, rare-earth, and transuranium elements [5][6][7], fire-retardants [8], and photochromic [9] and luminescent materials [10]. Phosphine oxides are successfully used as building blocks, e.g., in the Wittig-Horner reaction [11][12][13][14], specifically, for the synthesis of substituted vitamin D 3 analogs [14].…”

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confidence: 99%

Reaction of secondary phosphine oxides with acylacetylenes

et al. 2010

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Secondary phosphine oxides reacted with 1-alkanoyl-2-phenylacetylenes in chemoselective fashion under mild conditions (20°C, THF) in the absence of a catalyst (diphenylphosphine oxide) or in the presence of potassium hydroxide [bis(2-phenylethyl)phosphine oxide] to give 1-alkyl-1-diphenyl(or 2-phenylethyl)-phosphoryl-3-phenylprop-2-yn-1-ols in up to 96% yield. The reaction of diphenylphosphine oxide with 1-alkanoyl-2-phenylacetylenes in the system KOH-THF (20°C) afforded not only adducts at the carbonyl group but also products of double α,β-addition at the triple bond, 2,3-bis(diphenylphosphoryl)-3-phenylpropan-1-ones.

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Triorganylphosphine oxides as high-performance fire retardants for polyvinyl chloride plastisols

Cited by 15 publications

References 1 publication

Improved Synthetic Route to Heteroleptic Alkylphosphine Oxides

Improved Synthetic Route to Heteroleptic Alkylphosphine Oxides

Structure of Tris[2-(4-pyridyl)ethyl]phosphine, Tris[2-(2-pyridyl)ethyl]phosphine, and Their Chalcogenides in Solution: Dipole Moments, IR Spectroscopy, and DFT Study

Reaction of secondary phosphine oxides with acylacetylenes

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