814-29-9Relevant articles and documents
Synthesis and reactivity of new organophosphorus compounds
Tyryshkin, Nickolay I.,Konovalov, Alexander I.,Gavrilov, Viktor V.,Polezhaeva, Nina A.
, p. 553 - 556 (1996)
Synthesis of functionally substituted organophosphorus compounds on the basis of reactions of the tri-n-butylphosphine/carbon disulfide, tri-n-butylphosphine/phenyltsothiocyanate, tris(dimethylamino)phosphine/phenylisothiocyanate adducts with a wide range of different dipolarophiles are reported. The development of application of S-Li tri-n-butylphosphonio-dithioformiate derivatives to the synthesis of new types of organophosphorus compounds are reported.
Revealing the Molecular Identity of Defect Sites on PbS Quantum Dot Surfaces with Redox-Active Chemical Probes
Hartley, Carolyn L.,Dempsey, Jillian L.
, p. 2655 - 2665 (2021)
Defects arising on the surfaces of semiconductor quantum dots (QDs) limit the applications of these otherwise promising materials. Efforts to rationally passivate these sites using chemical methods, however, are limited by a lack of molecular-level understanding of surface defects. Herein, we report the application of redox-active chemical probes (E - ′ = -0.48 to -1.9 V vs Fc+/0) coupled with spectroscopic tools (nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), and UV-vis-NIR) to gain insight into the molecular-level nature and reactivity of defects at PbS QD surfaces. First, Pb ion-based traps coordinated by oleate ligands are studied by reaction with outer-sphere reductants, wherein reduction of a subpopulation of Pb2+ ions promotes ligand displacement. We observe a correlation between this reactivity and QD size, wherein minimal ligand displacement occurs in small QDs (2.6 nm) but up to ca. 15% of ligands are displaced with larger QDs (>4 nm). The strength of the reductant also has a significant impact; with QD size held constant, more potent reductants induce a higher extent of ligand displacement than mild reductants. Finally, chalcogenide-based defects (disulfides) are interrogated with selective trialkylphosphine reagents. Comparison of QD reactivity with phosphine probes reveals that large PbS QDs possess a greater proportion of native disulfide defects than small QDs. Collectively, this work yields insight into the identities, likely structural environments and reduction potentials of targeted defect sites, thus providing a detailed picture - and roadmap for passivation - of common QD surface defects.
Kinetic study on the reaction of tributylphosphine with methylviologen. Reactivity of the phosphine radical cation intermediate towards nucleophiles
Yasui, Shinro,Shioji, Kosei,Tsujimoto, Munekazu,Ohno, Atsuyoshi
, p. 855 - 862 (1999)
Tributylphosphine, Bun3P (BP), was reacted with 1.1′-dimethyl-4,4′-bipyridinium (methylviologen; MV2+) in the presence of an alcohol or thiol (RXH; X = O, S) in acetonitrile under an argon atmosphere at 50 °C, which resulted in the gradual formation of the one-electron reduced form of the MV2+, MV+. Meanwhile, BP was oxidized to tributylphosphine oxide (BP-O). The increase in the amount of MV+, which was followed spectrophotometrically with BP and RXH being in large excess, did not obey first-order kinetics. The observation, along with the results from product analysis, shows that single-electron transfer (SET) takes place from BP to MV2+ to generate tributylphosphine radical cation BP·+, as well as MV+, and the resulting BP·+ undergoes ionic reaction with RXH and back electron transfer from MV+ in comparable efficiency. A regression analysis of the kinetic data gave the relative value of the second-order rate constant, kNurel, for the ionic reaction of BP·+ with RXH. Comparison of the kNurel values thus obtained for reactions with various RXH's shows that the reaction of BP·+ with nucleophile RXH is governed by both steric and electronic factors of RXH. The activation energy Ea of the reaction was found to be significantly large, which is in contrast to previous observations that ionic reactions of carbon radical cations with nucleophiles usually have very small values of Ea.
Phosphorylation of 3,4-dichloro-5-hydroxy-2(5H)-furanone with tributylphosphine
Polezhaeva,Volodina,Kalinina,Sahibullina,Chmutova,Galkin,Cherkasov
, p. 1202 - 1206 (2002)
The reaction of 3,4-dichloro-5-hydroxy-2(5H)-furanone with 2 mol of tributylphosphine involves substitution of both chlorine atoms to form an unstable diphosphonium salt. The latter undergoes partial hydrolysis with cleavage of one of the P-C bonds, yield
Reversible Capture and Release of a Ligand Mediated by a Long-Range Relayed Polarity Switch in a Urea Oligomer
Clayden, Jonathan,Morris, David T. J.,Wales, Steven M.
supporting information, p. 2841 - 2846 (2022/02/23)
Ethylene-bridged oligoureas characterized by a continuous, switchable chain of hydrogen bonds and carrying a binding site (an N,N′-disubstituted urea) for a hydrogen-bond-Accepting ligand (a phosphine oxide) were synthesized. These oligomers show stronger ligand binding when the binding site is located at the hydrogen-bond-donating terminus than when the same binding site is at the hydrogen-bond-Accepting terminus. An acidic group at the terminus remote from the binding site allows hydrogen bond polarity, and hence ligand binding ability, to be controlled remotely by a deprotonation/reprotonation cycle. Addition of base induces a remote conformational change that is relayed through up to five urea linkages, reducing the ability of the binding site to retain an intermolecular association to its ligand, which is consequently released into solution. Reprotonation returns the polarity of the oligomer to its original directionality, restoring the function of the remote binding site, which consequently recaptures the ligand. This is the first example of a synthetic molecular structure that relays intermolecular binding information, and these dynamic foldamer structures are prototypes of components for chemical systems capable of controlling chemical function from a distance.
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
Application and method for extracting lithium from salt lake brine
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Paragraph 0067-0071, (2021/05/05)
The invention discloses application of an alkylphosphine oxide compound and a method for extracting lithium from salt lake brine, and belongs to the technical field of extraction. An organic phase ofan extraction system for the method comprises the alkylphosphine oxide compound, and the alkylphosphine oxide compound has phosphine oxide groups and is coordinated with Li+ to extract Li+. Compared with the prior art, the extraction method has the characteristics of low cost, simplicity in operation, high extraction efficiency, cleanness, environmental friendliness and the like, and most importantly, the extraction agent can not be hydrolyzed under the extraction condition, can be effectively used for a long time, and has important application value.
Selective C-P(O) Bond Cleavage of Organophosphine Oxides by Sodium
Zhang, Jian-Qiu,Ikawa, Eiichi,Fujino, Hiroyoshi,Naganawa, Yuki,Nakajima, Yumiko,Han, Li-Biao
, p. 14166 - 14173 (2020/11/13)
Sodium exhibits better efficacy and selectivity than Li and K for converting Ph3P(O) to Ph2P(OM). The destiny of PhNa co-generated is disclosed. A series of alkyl halides R4X and aryl halides ArX all react with Ph2P(ONa) to produce the corresponding phosphine oxides in good to excellent yields.
Cross-linked poly(4-vinylpyridine-N-oxide) as a polymer-supported oxygen atom transfer reagent
Bauer, Anna M.,Ramey, Erin E.,Oberle, Kjersti G.,Fata, Gretchen A.,Hutchison, Chloe D.,Turlington, Christopher R.
supporting information, (2019/10/02)
Oxygen atom transfer (OAT) reagents are common in biological and industrial oxidation reactions. While many heterogeneous catalysts have been utilized in OAT reactions, heterogeneous OAT reagents have not been explored. Here, cross-linked poly(4-vinylpyridine-N-oxide), called x-PVP-N-oxide, was tested as a heterogeneous OAT reagent and its oxidation chemistry compared to its molecular counterpart, pyridine-N-oxide. The insoluble oxidant x-PVP-N-oxide demonstrated comparable reactivity to pyridine-N-oxide in direct oxidation reactions of phosphines and phosphites in acetonitrile, but x-PVP-N-oxide did not react in other solvents. The polymer backbone of x-PVP-N-oxide, however, allowed for easy filtering and recycling in sequential oxidation reactions. In addition, x-PVP-N-oxide was tested as the stoichiometric oxidant in a copper-catalyzed OAT reaction to α-diazo-benzeneacetic acid methyl ester. The heterogeneous oxidant was much less reactive than pyridine-N-oxide, indicating that interaction with the metal catalyst was challenging. These results demonstrated a proof-of-concept that recyclable, polymer-supported OAT reagents could be a viable OAT reagents in direct oxidation reactions without metal catalysts.
Single-stage synthesis of alkyl-H-phosphinic acids from elemental phosphorus and alkyl bromides
Gusarova, Nina K.,Sutyrina, Anastasiya O.,Kuimov, Vladimir A.,Malysheva, Svetlana F.,Belogorlova, Natalia A.,Volkov, Pavel A.,Trofimov, Boris A.
, p. 328 - 330 (2019/06/13)
Elemental phosphorus (red or white) reacts with alkyl bromides at 60–62 °C in the phase-transfer catalytic system KOH/H2O/PhMe/Et3BnNCl to afford alkyl-H-phosphinic acids in up to 47% yield.
