cas 855-38-9, TRIS(4-METHOXYPHENYL)PHOSPHINE

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Photochemical transformation of chlorobenzenes and white phosphorus into arylphosphines and phosphonium salts
Chlorobenzenes are important starting materials for the preparation of commercially valuable triarylphosphines and tetraarylphosphonium salts, but their use for the direct arylation of elemental phosphorus has been elusive. Here we describe a simple photochemical route toward such products. UV-LED irradiation (365 nm) of chlorobenzenes, white phosphorus (P4) and the organic superphotoreductant tetrakis(dimethylamino)ethylene (TDAE) affords the desired arylphosphorus compounds in a single reaction step.
Gschwind, Ruth M.,Mende, Michael,Scott, Daniel J.,Streitferdt, Verena,Till, Marion,Wolf, Robert
supporting information
p. 1100 - 1103
(2022/02/03)

A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
García-Domínguez, Andrés,Gonzalez, Jorge A.,Leach, Andrew G.,Lloyd-Jones, Guy C.,Nichol, Gary S.,Taylor, Nicholas P.
supporting information

(2022/01/04)

Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight
Detailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′-di-tert-butyl-2,2′-bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
Cammarata, Jose,Gschwind, Ruth M.,Lennert, Ulrich,Rothfelder, Robin,Scott, Daniel J.,Streitferdt, Verena,Wolf, Robert,Zeitler, Kirsten
supporting information
p. 24650 - 24658
(2021/10/14)

Lewis Acidic Boranes, Lewis Bases, and Equilibrium Constants: A Reliable Scaffold for a Quantitative Lewis Acidity/Basicity Scale
A quantitative Lewis acidity/basicity scale toward boron-centered Lewis acids has been developed based on a set of 90 experimental equilibrium constants for the reactions of triarylboranes with various O-, N-, S-, and P-centered Lewis bases in dichloromethane at 20 °C. Analysis with the linear free energy relationship log KB=LAB+LBB allows equilibrium constants, KB, to be calculated for any type of borane/Lewis base combination through the sum of two descriptors, one for Lewis acidity (LAB) and one for Lewis basicity (LBB). The resulting Lewis acidity/basicity scale is independent of fixed reference acids/bases and valid for various types of trivalent boron-centered Lewis acids. It is demonstrated that the newly developed Lewis acidity/basicity scale is easily extendable through linear relationships with quantum-chemically calculated or common physical–organic descriptors and known thermodynamic data (ΔH (Formula presented.)). Furthermore, this experimental platform can be utilized for the rational development of borane-catalyzed reactions.
Mayer, Robert J.,Hampel, Nathalie,Ofial, Armin R.
supporting information
p. 4070 - 4080
(2021/01/29)

The Trityl-Cation Mediated Phosphine Oxides Reduction
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.).
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information
p. 3035 - 3043
(2021/05/10)

Synthesis method of phosphine (III) compound
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.
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Paragraph 0020

(2021/11/27)

Synthesis method of triphenylphosphine derivative tri-(R-phenyl) phosphine
The invention relates to a synthesis method of a triphenylphosphine derivative tri-(R-phenyl) phosphine. The synthesis method comprises the following steps: adding magnesium chips, a solvent and R-substituted halobenzene into a reaction kettle under the protection of nitrogen, initiating a reaction at a proper temperature, and dropwise adding an R-substituted halobenzene solution to synthesize anintermediate; dropwise adding a phosphorus trichloride solution to complete a Grignard reaction; dropwise adding diluted hydrochloric acid for hydrolysis after negative-pressure desolvation; and carrying out post-treatment to obtain TRPP. According to the method, the tri-(R-phenyl) phosphine of which the purity is greater than 99% is obtained with high selectivity and high yield.
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Paragraph 0056-0062

(2020/11/09)

Organic long afterglow material with photoactivation characteristic as well as preparation method and application thereof
The invention discloses an organic long afterglow material with photoactivation characteristic, and a preparation method and application thereof. The chemical structure of the material has a general formula; and R in the formula is H, F, OCH3. According to the invention, the series of compounds are prepared by taking a triphenylphosphine oxide derivative as a research object and connecting different substituents to three benzene ring para-positions of triphenylphosphine oxide. after controlling of the ultraviolet irradiation time, the phosphorescence service life and the intensity of the series of materials are obviously improved. And in combination with different dynamic adjustability, multiple information encryption applications are realized.
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Paragraph 0056-0061

(2020/09/09)

Ir(III)-catalyzed direct C-H functionalization of arylphosphine oxides: A strategy for MOP-type ligands synthesis
Diazo compounds as coupling partners are efficiently applied to Ir(III)-catalyzed direct C-H functionalization of arylphos-phine oxides. Involving C-H activation, carbene insertion, and tautomerism, this reaction proceeds under mild conditions, thus proving an approach to the synthesis of MOP-type ligand precursor in a single step. The utility of this transformation has been further demonstrated in ligand synthesis as well as in the construction of phosphole framework.
Liu, Zhong,Wu, Ji-Qiang,Yang, Shang-Dong
supporting information
p. 5434 - 5437
(2017/11/06)

Metal-Free Reduction of Phosphine Oxides, Sulfoxides, and N-Oxides with Hydrosilanes using a Borinic Acid Precatalyst
The general reduction of phosphine oxides, sulfoxides, and amine N-oxides was achieved by combining bis(2-chlorophenyl)borinic acid with phenylsilane. The reaction was shown to tolerate a wide range of substrates and could be performed under mild conditions, with only 2.5 mol % of the easily synthesized catalyst. Mechanistic investigations pointed to a key borohydride as the real catalyst and at bis(2-chlorophenyl)borinic acid as a precatalyst.
Chardon, Aurélien,Maubert, Orianne,Rouden, Jacques,Blanchet, Jér?me
p. 4460 - 4464
(2017/11/22)

Mild Reduction of Phosphine Oxides with Phosphites To Access Phosphines
A new method for the iodine-catalyzed reduction of phosphine oxides with phosphites at room temperature is reported. The mild reaction conditions, scalability, and simple purification requirements render it a method of choice for the large-scale production and facile regeneration of a variety of phosphines. Mechanistic studies, supported by DFT calculations of the oxygen transfer between the starting phosphine oxide and the phosphite reagent, are also presented. Such transmutations of phosphorus species were previously unknown.
Li, Peng,Wischert, Raphael,Métivier, Pascal
supporting information
p. 15989 - 15992
(2017/11/01)

Atom Economic Ruthenium-Catalyzed Synthesis of Bulky β-Oxo Esters
Ruthenium complexes with the formulae Ru(CO)2(PR3)2(O2CPh)2 [6a-h; R=n-Bu, p-MeO-C6H4, p-Me-C6H4, Ph, p-Cl-C6H4, m-Cl-C6H4, p-CF3-C6H4, m,m′-(CF3)2C6H3] were prepared by treatment of triruthenium dodecacarbonyl [Ru3(CO)12] with the respective phosphine and benzoic acid or by the conversion of Ru(CO)3(PR3)2 (8e-h) with benzoic acid. During the preparation of 8, ruthenium hydride complexes of type Ru(CO)(PR3)3(H)2 (9g, h) could be isolated as side products. The molecular structures of the newly synthesized complexes in the solid state are discussed. Compounds 6a-h were found to be highly effective catalysts in the addition of carboxylic acids to propargylic alcohols to give valuable β-oxo esters. The catalyst screening revealed a considerably influence of the phosphine′s electronic nature on the resulting activities. The best performances were obtained with complexes 6g and 6h, featuring electron-withdrawing phosphine ligands. Additionally, catalyst 6g is very active in the conversion of sterically demanding substrates, leading to a broad substrate scope. The catalytic preparation of simple as well as challenging substrates succeeds with catalyst 6g in yields that often exceed those of established literature systems. Furthermore, the reactions can be carried out with catalyst loadings down to 0.1mol% and reaction temperatures down to 50 C.
Jeschke, Janine,Korb, Marcus,Rüffer, Tobias,G?bler, Christian,Lang, Heinrich
supporting information
p. 4069 - 4081
(2016/01/25)

Reduction of phosphine oxides to the corresponding phosphine derivatives in Mg/Me3SiCl/DMI system
Direct reductions of phosphine oxides to the corresponding phosphines were performed successfully by using Mg/Me3SiCl/DMI system. The reduction proceeded under mild conditions and was applicable to a wide range of phosphine oxides; triarylphosphine oxides, alkyldiarylphosphine oxides, and dialkylarylphosphine oxides gave the corresponding phosphines in good to excellent yields.
Kuroboshi, Manabu,Kita, Toshihito,Aono, Asuka,Katagiri, Toshimasa,Kikuchi, Seiya,Yamane, Syoko,Kawakubo, Hiromu,Tanaka, Hideo
p. 918 - 920
(2015/02/05)

Highly efficient reduction of tertiary phosphine oxides and sulfides with amine-assisted aluminum hydrides under mild conditions
Reduction of tertiary phosphine oxides and sulfides into the corresponding phosphines with amine-assisted aluminum hydrides has been studied. The method is characterized by mild conditions, short reaction time, high efficiency, and expanded substrate scope. The new method is an alternative to the currently used methods of reducing phosphine oxides or recycling phosphines engaged in organic reactions.
Yang, Shuyan,Han, Xinxin,Luo, Minmin,Gao, Jing,Chu, Wenxiang,Ding, Yuqiang
p. 1156 - 1160
(2015/06/30)

Metal-free reduction of tertiary phosphine oxides with Hantzsch ester
The (COCl)2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and alkyldiarylphosphine oxides to produce the corresponding tertiary phosphines in good to excellent yields. This new finding provides a practical, convenient and metal-free method for the reduction of tertiary phosphine oxides to tertiary phosphines, and shows potential application in organic synthesis.
Zhang, Tong-Xin,Zhang, Wei-Xi,Luo, Mei-Ming
p. 176 - 178
(2014/02/14)

Highly Active and Selective Ethylene Oligomerization Catalyst and Method of Preparing Hexene or Octene Using the Same
This invention relates to a chromium complex compound for selective ethylene oligomerization including a chiral ligand, and to a method of selectively preparing 1-hexene or 1-octene from ethylene using the same.
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(2012/06/01)

Ethylene oligomerization catalyst systems having enhanced selectivity
Disclosed herein is a catalyst system for selective oligomerization of ethylene, which comprises a P—C—C—P frame-work ligand, which is (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4), and a chromium-based metal compound. Also disclosed is a method of greatly enhancing the activity and selectivity of oligomerization, such as trimerization or tetramerization, using a ligand having a specific steric arrangement structure.
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Page/Page column 15

(2013/02/27)

Application of Mitsunobu reagents to redox Isomerization of CF 3-containing propargylic alcohols to (E)-α,β-enones
Isomerization of CF3-containing secondary propargylic alcohols proceeds with excellent E selectivity by treatment with Mitsunobu reagents, tris- (p-methoxyphenyl)phosphine (TMPP), and 1,1′-(azodicarbonyl) dipiperidine (ADDP) in the presence of phenol.
Watanabe, Yohsuke,Yamazaki, Takashi
supporting information; experimental part
p. 1957 - 1960
(2011/06/20)

Electroreduction of triphenylphosphine oxide to triphenylphosphine in the presence of chlorotrimethylsilane
Electroreduction of triphenylphosphine oxide to triphenylphosphine in an acetonitrile solution of tetrabutylammonium bromide in the presence of chlorotrimethylsilane was performed successfully in an undivided cell fitted with a zinc anode and a platinum cathode under constant current. A plausible mechanism involving, (1) one-electron reduction of triphenylphosphine oxide generating the corresponding anion radical [Ph3P-O-], (2) subsequent reaction with chlorotrimethylsilane affording the (trimethylsiloxy)triphenylphosphorus radical [Ph3P-OSiMe 3], and (3) further one-electron reduction followed by P-O bond fission leading to triphenylphosphine is proposed. In a similar manner, electroreduction of some triarylphosphine oxides and alkyldiarylphosphine oxides was executed to give the corresponding phosphine derivatives in good to moderate yields. Georg Thieme Verlag Stuttgart · New York.
Kawakubo, Hiromu,Kuroboshi, Manabu,Yano, Tomotake,Kobayashi, Kazuma,Kamenoue, Syogo,Akagi, Tomomi,Tanaka, Hideo
scheme or table
p. 4091 - 4098
(2012/01/12)

PROCESS FOR PRODUCTION OF PHOSPHINE DERIVATIVE FROM PHOSPHINE OXIDE DERIVATIVE
Disclosed is a process for producing a phosphine derivative from a phosphine oxide derivative, which comprises the following steps: (I) mixing a phosphine oxide derivative represented by formula (1) with a chlorinating agent in a polar organic solvent to cause the reaction between these components; and (II-1) adding a salt of a metal having an ionization tendency equal to or lower than that of aluminum to the reaction mixture and carrying out the reductive reaction in the presence of aluminum or (II-2) subjecting the reaction mixture to electrolytic reduction, thereby producing a phosphine derivative represented by formula (2). ArnR3-nP═O (1) ArnR3-nP (2) In formulae (1) and (2), Ar represents an aryl group such as a phenyl group, a phenyl group having a substituent, a heteroaromatic ring group, and a heteroaromatic ring group having a substituent; R represents an aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a substituent; and n represents an integer of 0 to 3.
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(2011/04/18)

ETHYLENE TETRAMERIZATION CATALYST SYSTEMS AND METHOD FOR PREPARING 1-OCTENE USING THE SAME
Disclosed herein is a method of preparing 1-octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromium-based catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a P—C—C—P backbone structure ligand represented by (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4).
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(2010/06/16)

Synthesis of symmetrical and unsymmetrical functionalized arylphosphines from chlorophosphines and organozinc reagents
A stepwise procedure allowing the formation of symmetrical arylphosphines is described. It relies on the use of preformed functionalized aromatic organozinc reagents to perform arylations of chlorophosphines. Some preliminary results concerning the synthesis of unsymmetrical diarylphenylphosphines through sequential coupling of organozinc species with dichlorophenylphosphine are also reported. Georg Thieme Verlag Stuttgart.
Le Gall, Erwan,Ben A?ssi, Karima,Lachaise, Isabelle,Troupel, Michel
p. 954 - 956
(2007/10/03)

synthesis and Solid-State Structure of Substituted Arylphosphine Oxides
We described the preparation and characterization of several new arylphosphine oxides, which are of interest as second-order nonlinear optical materials. (4-Aminophenyl)diphenylphosphine oxide (1a), bis(4-aminophenyl)phenylphosphine oxide (2a), and (4-aminophenyl)bisphosphine oxide (5) were prepared by addition of aryl Grignard and organolithium reagents containing protected amines to phosphorus oxyhalides.Alternatively, 1a was prepared by treatment of (4-bromophenyl)diphenylphosphine oxide with azidomethyl phenyl sulfide, followed by hydrolysis. (4-Aminophenyl)(4'-nitrophenyl)phenylphosphine oxide (6) was prepared by nucleophilic aromatic substitution of bis(4-fluorophenyl)phenylphosphine oxide to give the corresponding dinitro compound, followed by selective mono-reduction.The X-ray crystal structure of (4-aminophenyl)diphenylphosphine oxide (1a), along with those of mono-, di-, and trihydroxy triphenylphosphine oxides 1b, 2b, and 3b, exhibit extensive intermolecular hydrogen bonding.The hydrogen bonding in 1a and 1b produces chains of arylphosphine oxide molecules with a head-to-tail alignment; the chains pack in an antiparallel manner to produce solid-state structures that display only slight deviations from centrosymmetry.
Whitaker, Craig M.,Kott, Kevin L.,McMahon, Robert J.
p. 3499 - 3508
(2007/10/02)

Sterically encumbered functional groups: An investigation of endo versus exo phosphoryl complexation using 1H and 31P NMR
The synthesis of phosphine oxide bifunctional macrocycles 1-4 is reported. Additionally, the X-ray crystal structures for exo-exo diyne 1 and endo-exo hosts 2 and 4 are presented. Assignment of the two phosphorus signals in the 31P NMR spectra of 2 and 4 and the aromatic proton signals in the 1H NMR spectra of 2 and 4 is reported. The complexation behavior of macrocycles 1-4 and precyclophane 8 with a variety of neutral organic guests and Ph2SnCl2 is investigated by using 1H and 31P NMR as investigative instrumental probes. Initial endo complexation is the preferred mechanism in the 1:2 complexation of 2 with guests, while initial exo complexation is preferred for the complexation of 4 with guests. 2 forms 1:2 complexes with pentafluorophenol, 2,6-dimethyl-4-nitrophenol, and acetic acid via initial exo complexation. Association constants determined from these experiments reveal that the exo phosphoryl binding site in 4 is higher than those in the other reported phosphine oxides. An X-ray crystal structure of the 1:1 complex of 4 with diphenyltin dichloride was obtained to explore this anomaly, and it is reported.
Friedrichsen, Bernard P.,Powell, Douglas R.,Whitlock, Howard W.
p. 8931 - 8941
(2007/10/02)

Tetra-arylfluorophosphoranes
A number of novel tetra-arylfluorophosphoranes have been synthesised.The most stable form of these compounds is the ionic form PR4+F- (R=aryl) although various other forms have been shown to exist including a molecular monomer PR4F and a dimer PR4+PR4F2-.The i.r. spectra of the ionic forms reveal strong P+...F- interactions.The fluorides are prepared via the hydrogendifluorides PR4+HF2- which contain distorted HF2- ions.
Brown, Stephen J.,Clark, James H.,Macquarrie, Duncan J.
p. 277 - 280
(2007/10/02)

Syntheses and Spectroscopic Investigations of Substituted cis- and trans-Dichlorobis(triphenylphospane)platinum(II) Compounds
Compounds of the type cis- and trans-dichlorobis(triphenylphosphane)platinum(II) (3) with substituents of different electronic character in the phenyl rings bonded to phosphorus have been synthesized.The coupling constants 1J and the chloro-platinum valence vibrational frequencies are demonstrated to be criteria for unambiguous discrimination between cis- and trans-configurations at platinum; a linear correlation exists between the sum of the ?-constants of the sustituents at the triphenylphosphane and the coupling constants 1J.
Brune, Hans Albert,Falck, Manfred,Hemmer, Reinhard,Schmidtberg, Guenter,Alt, Helmut G.
p. 2791 - 2802
(2007/10/02)

The basicity of phosphines
The basicities of the triarylphosphines P(4-XC6H4)3 (X = Cl, F, H, CH3, CH3O, (CH3)2N), P(3-CH3C6H4)3, and P(2-CH3C6H7)3 as well as the trialkylphosphines P(t-Bu)3 and PCy3 have been measured by the nitromethane titration method.The range of basicity available by aryl substitution is very large, being pKa = 8. 65 for X = (CH3)2N to 1.03 for X = Cl.The most basic phosphine is P(t-Bu)3 whose pKa = 11.40.The measured basicities correlate well wit ?p, ?Φ, and ν as well as with the lone pair ionisation potentials of the triarylphosphines.Generally the 1H,31P, and 13C nmr spectral parameters of the free and protonated phosphines do not correlate well with pKa.
Allman, Tim,Goel, Ram G.
p. 716 - 722
(2007/10/02)