5931-53-3Relevant academic research and scientific papers
Palladium-Catalyzed C-P(III) Bond Formation by Coupling ArBr/ArOTf with Acylphosphines
Chen, Xingyu,Wu, Hongyu,Yu, Rongrong,Zhu, Hong,Wang, Zhiqian
, p. 8987 - 8996 (2021/06/30)
Palladium-catalyzed C-P bond formation reaction of ArBr/ArOTf using acylphosphines as differential phosphination reagents is reported. The acylphosphines show practicable reactivity with ArBr and ArOTf as the phosphination reagents, though they are inert to the air and moisture. The reaction affords trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance. This reaction discloses the acylphosphines' capability as new phosphorus sources for the direct synthesis of trivalent phosphines.
Synthesis method of phosphine (III) compound
-
Paragraph 0020, (2021/11/27)
The invention aims to provide an aryl phosphine oxide compound as a raw material, wherein P=O keys are activated by an acid anhydride and alkali is continued. The preparation of the phosphine (III) compound is carried out under the action of a crown ether and a reducing agent. The method has the advantages of cheap and easily available raw materials, simple operation, high atomic economy and the like. Compared with a traditional reduction mode, the method is ingenious in design, waste emission is reduced, separation of intermediate products is omitted, and related reagents such as silicon hydrogen, aluminum, boron and the like with higher price can be avoided. And the reaction suitability is extensive.
Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
Arockiam, Percia Beatrice,Lennert, Ulrich,Graf, Christina,Rothfelder, Robin,Scott, Daniel J.,Fischer, Tillmann G.,Zeitler, Kirsten,Wolf, Robert
supporting information, p. 16374 - 16382 (2020/11/03)
Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible-light-driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.
NOVEL CERIUM COMPLEX, AND LIGHT EMITTING MATERIAL
-
Paragraph 0071; 0072, (2019/10/01)
PROBLEM TO BE SOLVED: To provide a novel cerium carbene complex suitable for LED phosphors, organic EL emission layer materials, wavelength conversion materials for solar cells, and wavelength conversion materials for agriculture facility, and a method of producing the same. SOLUTION: The present invention provides a cerium complex with trivalent cerium coordinated with a carbene compound; particularly, a cerium complex in which the carbene compound coordinated to trivalent cerium being represented by formula (1). (R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 each represent a hydrogen atom, or a C1-20 hydrocarbon group, or a hydrocarbon group containing an oxygen atom or a phosphorus atom, where they may be bound to each other, to form a ring. R11, R12 each represent a hydrogen atom or a C1-20 hydrocarbon group, where they may be bound to each other, to form a ring. x is an integer of 0 to 10). SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
Preparing method of triarylphosphine compound
-
Paragraph 0028; 0029; 0030; 0031, (2019/07/16)
The invention belongs to the technical field of medicine and natural compound chemical intermediates and relevant chemistry, and provides a preparing method of a triarylphosphine compound. According to the preparing method, a diphenylphosphine compound and aryl halide serve as raw materials, participation of transition metal catalysts is not needed, and the triarylphosphine compound is constructedin one step under the heating condition. The preparing method has the advantages that according to the reaction, the metal or non-metal catalysts are not needed for catalytic reactions, the triarylphosphine compound is clean and free of pollution, the reaction condition is mild, the operation and aftertreatment are simple, and the substrate compatibility is good.
A practical synthesis of unsymmetrical triarylphosphines by heterogeneous palladium(0)-catalyzed cross-coupling of aryl iodides with diphenylphosphine
Xu, Zhaotao,Wang, Pingping,Chen, Qiurong,Cai, Mingzhong
, p. 50 - 58 (2018/04/23)
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in DMAc at 130 °C in the presence of 1.0 mol% of MCM-41-supported tridentate nitrogen palladium(0) complex [MCM-41-3N-Pd(0)] with KOAc as base, yielding a variety of unsymmetrical triarylphosphines in good to excellent yields. The turnover frequency (TOF) of the catalyst can reach 30.67 h?1. This new heterogeneous palladium(0) catalyst could easily be prepared by a simple procedure from commercially readily available reagents, and exhibited the same catalytic activity as homogeneous Pd(OAc)2 or Pd(PPh3)4, and could be recovered by filtration of the reaction solution and recycled at least seven times without significant loss of catalytic activity.
An efficient heterogeneous cross-coupling of aryl iodides with diphenylphosphine catalyzed by copper (I) immobilized in MCM-41
Fang, Zhiqiang,Cai, Mingzhong,Lin, Yang,Zhao, Hong
, (2018/07/31)
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in toluene at 115?°C in the presence of 10?mol% of phenanthroline-functionalized MCM-41-supported copper (I) complex (Phen-MCM-41-CuI) with Cs2CO3 as base, yielding various unsymmetric triarylphosphines in good to excellent yields. This protocol can tolerate a wide range of functional groups and does not need the use of expensive additives or harsh reaction conditions. This heterogeneous Cu (I) catalyst exhibited the same catalytic activity as homogeneous CuI/Phen system, and could easily be recovered by a simple filtration of the reaction solution and recycled up to seven times without significant loss of activity.
Electrophilic Phosphonium Cation-Mediated Phosphane Oxide Reduction Using Oxalyl Chloride and Hydrogen
Stepen, Arne J.,Bursch, Markus,Grimme, Stefan,Stephan, Douglas W.,Paradies, Jan
supporting information, p. 15253 - 15256 (2018/10/24)
The metal-free reduction of phosphane oxides with molecular hydrogen (H2) using oxalyl chloride as activating agent was achieved. Quantum-mechanical investigations support the heterolytic splitting of H2 by the in situ formed electrophilic phosphonium cation (EPC) and phosphane oxide and subsequent barrierless conversion to the phosphane and HCl. The reaction can also be catalyzed by the frustrated Lewis pair (FLP) consisting of B(2,6-F2C6H3)3 and 2,6-lutidine or phosphane oxide as Lewis base. This novel reduction was demonstrated for triaryl and diaryl phosphane oxides providing access to phosphanes in good to excellent yields (51–93 %).
High- and low-spin chelate complexes of iron featuring κ-C,X-CH2C6H4X (X?= NMe2, PMe2, PPh2) and κ-C,P-CH2PMe2 ligands
Jacobs, Brian P.,Wolczanski, Peter T.,MacMillan, Samantha N.
, p. 132 - 139 (2017/09/12)
Several C,X-chelate complexes of iron were generated via standard metathetical procedures. Treatment of FeCl2 and LnFeCl2 (L = Me2IPr, n = 1; PMe3, n = 2) with anionic equivalents o-LiCH2C6H4NMe2, o-LiCH2C6H4PPh2, and LiCH2PMe2 led to the preparation of [Fe(o-CH2C6H4NMe2)]2(κ-μ-CH2,N-o-CH2C6H4NMe2)2 (1, X-ray), [fac-Fe(κ-C,P-o-CH2C6H4PPh2)3][Li(TMEDA)2] (2, X-ray), (Me2IPr)Fe(CH2C6H4-o-NMe2)2 (3-C,N), [(Me2IPr)2Fe](μ-κ-C,P-CH2PMe2)2[Fe(κ-C,P-CH2PMe2)2] (4, X-ray), and (PMe3)2Fe(κ-C,P-CH2PMe2)2 (5). CH-Bond activation of cis-(Me3P)4FeMe2 with o-CH3C6H4PMe2 led to the generation of trans,cis-(PMe3)2Fe(κ-C,P-CH2C6H4-o-PMe2)2 (6). Exposure of these compounds to [Cp2Fe][PF6], a 1e? oxidant, or AdN3, here construed as a 2e? oxidant, led to degradation in all cases, usually with the generation of carbon-carbon coupled ligands as byproducts. The inability of these systems to permit access to higher iron oxidation states is discussed.
Ligand-free palladium catalyzed phosphorylation of aryl iodides
Nowrouzi, Najmeh,Keshtgar, Saba,Bahman Jahromi, Enayatollah
, p. 348 - 350 (2016/01/12)
A reusable ligand-free palladium catalyzed phosphorylation of aryl iodides using PdCl2/tetrabutylammonium bromide is described. Functionalized triarylphosphines were obtained in good to excellent yields in the absence of external reductants and supporting ligands.
