Triphenylphosphine-catalyzed isomerization of alkynyl ketones in aqueous solution

An efficient isomerization of alkynyl ketones to (E,E)-diene ketones was developed. The reaction catalyzed by 20 mol% triphenylphosphine in aqueous media gave the desired products in good yields.

An efficient chemoselective synthesis of O-vinylaryl systems using acetylenic esters and dihydroxybenzenes in the presence of triphenylphosphine or alkyl isocyanides

The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.

Synthesis,Structural Characterization and Catalytic Activity of Copper(Ⅰ)Complexes with Triphenylphosphine and Pyridine Derivatives

Two new Cu（Ⅰ） complexes [CuCl（3-PyOH）（PPh_3）_2]（1） and [Cu_2（μ-Cl）_2（4-Stpy）（Ph_3P）_3]（2）（PyOH = hydroxypyridine; stpy = styrylpyridine） with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945（7）, b = 37.266（2）, c = 10.9461（7） A, β = 116.0750（10）°, V = 3625.3（4） A^3, Z = 4, D_c = 1.350 Mg/cm^（-3）, μ = 0.801 mm^（-1）, F（000） = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections（I 〉 2σ（I））, R（all data） = 0.0413, wR（all data） = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290（3）, b = 20.388（5）, c = 24.092（6） A, β = 102.028（4）°, V = 5424（2） A^3, Z = 4, D_c = 1.428 Mg/cm^（-3）, μ = 1.016 mm^（-1）, F（000） = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections（I 〉 2σ（I））, R（all data） = 0.0716, wR（all data） = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu（I） complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.

Triphenylphosphine Stabilized Silver Carboxylates

A series of novel triphenylphosphine stabilized silver carboxylates, potential precursors for CVD growth of ultrafast interconnection link in microelectronic devices, have been prepared and characterized.

Synthesis and Structural Characterization of a New One-dimensional Infinite Chain of Silver(I) Complex with Triphenylphosphine

The reaction of triphenylphosphine with AgNO3 yielded an unusual nitrate anion bridging one-dimensional infinite chain [Ag(PPh3)NO3] in which the silver(I) atom is three-coordinated by one P atom of triphenylphosphine and two O atoms of two bridging nitrate anions to form a scalene triangle. The complex [Ag(PPh3)NO3] crystallizes in the monoclinic system, space group P21/c with a = 10.281(2), b = 18.596(5), c = 9.180(2) , = 90.60(1), V = 1755.1(7) 3, Z = 4, Mr = 432.15, Dc = 1.635 g/cm3, F(000) = 864 and = 1.254 mm-1. The final R = 0.0606 and wR = 0.1400 for 2188 observed reflections with I > 2(I) out of 3057 unique ones (Rint = 0.0539). IR and elemental analysis of the complex are characterized.

A NOVEL SYNTHETIC METHOD AND STRUCTURE OF TETRAKIS(BENZOATE)BIS(TRIPHENYLPHOSPHINE OXIDE)DICOPPER(II).OXIDATIVE ADDITION OF DIBENZOYL ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metallic copper with triphenylphosphine in a mixed solvent(acetone,dichloromethane and trichloromethane),and affords the binuclear copper complex (Cu(C_6H_5COO)_2(OPPh_3))_2.Crystals are monoclinic,space group A_2/a,with cell parameters,a=24.337(3),b=10.566(1),c=21.579(2),β= 93.18(1)°, V=5540(1)~3,Z=4,R=0.042,and Rw=0.044 for 5872 observed reflections. Each copper ion is coordinated by four bridging benzoato ligands and one triphenylphosphine oxide group to form binuclear complexes.

Asymmetric Tetrahedral Cadmium Complex：Bis［triphenylphosphine］cadmium（Ⅱ）Diiodide

The structure of the title complex, [Cd (PPh_3)_2I_2], was determined by X-ray diffraction with crystallographic data as follows: C_36H_30CdI_2P_2, Mr=890. 75, monoclinic, space group P2_1/a, a=18. 367(3), b=10. 300(3), c=19.339 (3) A, β=111. 68(1)°; V=3400(1) A￣3, Z=4, D_x= 1. 74 g/cm￣3, P=25. 5 cm￣(-1),F(000)=1720, R=0. 0470, R_w=0. 049. The coordination polyhedron of each Cd atom is a distorted tetrahedron consisting of two P atoms from two triphenylphosphine groups and two iodine anions. The molecule has no C_2 symmetry with two unequal Cd -P bonds due to the presence of the bulky size of triphosphine.

Triphenylphosphine and sodium iodide: a new catalyst combination to rival precious metal complexes in visible light photoredox catalysis

Photoredox catalysis has changed the landscape of modern synthetic organic chemistry by prompting a dramatic increase in research activity into reactions that proceed through free radical intermediates.

Phase separation morphology and mode II interlaminar fracture toughness of bismaleimide laminates toughened by thermoplastics with triphenylphosphine oxide group

Toughness improvement of bismaleimide（BMI）resin is very important for its application in composite materials.Blending with

An effcient,rapid and facile procedure for conversion of aldoximes to nitriles using triphenylphosphine and N-halo sulfonamides

N,N,N＇,N＇-Tetrabromobenzene-1,3-disulfonamide （TBBDA）/triphenylphosphine and N,N,N＇,N＇-tetra- chlorobenzene-1,3-disulfonamide （TCBDA）/triphenylphosphine have been introduced as highly efficient systems for the versatile conversion of aldoxime derivatives into nitriles. The process reported here is operationally simple and reactions have been mildly performed in dichloromethane at room temperature.

STUDIES ON THE EXTRACTION MECHANISM OF GOLD (Ⅲ) FROM HYDROCHLORIC ACID MEDIUM BY TRIPHENYLPHOSPHINE OXIDE (TPPO)

In studies on the extraction chemistry of gold, the extractants of alcohols, ethers, ketones and amines are widely used. The neutral extractants tributylphosphate (TBP) and trioctylphosphine oxide (TPPO) have been widely applied. A few experiments on the synthesis of solid complexes of transition metal ions with TPPO have been car-

Triphenylphosphine-Catalyzed Michael Addition of Alcohols to Acrylic Compounds

A facile triphenylphosphine-catalyzed Michael addition of alcohols to acrylic compounds was described. The reaction was carried out in open air at refluxing temperature in the presence of 10 mol% PPh3. Michael addition of saturated and unsaturated alcohols to acrylonitrile or acrylates has been examined. The reaction gave β-alkoxy derivatives with isolated yields of 5%-79%. PPh3 is cheaper and more stable than those trialkylphosphines previously used for the similar reactions, and the products can be easily separated from the reaction mixture via distillation.

Triphenylphosphine as Reducing Agent for Copper(II)-catalyzed AGET ATRP

Triphenylphosphine （TPP） was used as reducing agent to continuously generate the Cu（I） activator in copper（II）- catalyzed activators generated by electron transfer atom transfer radical polymerization （AGET ATRP）. For example, the polymers prepared with a molar ratio of [MMA]0/[EBiB]0/[CuC12]o/[PMDETA]0/[TPP]o = 500/1/0.1/0.5/0.5 had controlled molecular weights and low molecular weight distribution （Mw/Mn） values （-1.2）. TPP as a commercial reducing agent provides a convenient copper-catalyzed AGET ATRP procedure for the preparation of well-defined polymers.

Three-component reaction of triphenylphosphine,dialkyl but-2-ynedioate and arylidene pivaloylacetonitrile for diastereoselective synthesis of densely substituted 2,3-dihydrofurans

The three-component reaction of triphenylphosphine,dialkyl but-2-ynedioate and arylidene pivaloylacetonitrile in dry methylene dichloride at room temperature resulted in unexpected densely substituted 1-（triphenyl-λ^5-phosphanylidene）ethyl）-2,3-dihydrofurans in satisfactory yields with high diastereoselectivity.The relative configuration of the 2,3-dihydrofurans was elucidated by determination of single crystal structures.

Effect of loading on the Ni_2P/Al_2O_3 catalysts for the hydrotreating reactions

The 80%Ni2P/Al2O3 catalysts were prepared by the phosphidation of corresponding 80%Ni/Al2O3 with triphenylphosphine in liquid phase and compared with the 60%Ni2P/Al2O3 for hydrotreating reactions. Both the60%Ni2P/Al2O3 and 80%Ni2P/Al2O3 in comparison exhibited the small and uniform Ni2 P particles（6.3 and8.4 nm,respectively）,high CO uptakes（305 and 345 μmol/g,respectively） and thus high activities for the hydrotreating reactions. After the hydrotreating reactions,the small and uniform Ni2 P particles were remained,although the CO uptakes on the used 60%Ni2P/Al2O3 and 80%Ni2P/Al2O3 were greatly decreased（to 68 and95 μmol/g,respectively） due to the incorporation of S into the Ni2 P surfaces. The 80%Ni2P/Al2O3 was found to be significantly more active than the 60%Ni2P/Al2O3 due to that the 80%Ni2P/Al2O3 possessed more,and more active Ni2 P sites than the 60%Ni2P/Al2O3,probably due to the less S incorporated in the 80%Ni2P/Al2O3 than in the 60%Ni2P/Al2O3 during the hydrotreating reactions.

Enhancing the activity,selectivity,and recyclability of Rh/PPh_(3) system‐catalyzed hydroformylation reactions through the development of a PPh_(3)‐derived quasi‐porous organic cage as a ligand

In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents that provide significant potential for homogeneous catalysis.Herein,we report a triphenylphosphine‐derived quasi‐porous organic cage(denoted as POC‐DICP)as an efficient organic molecular cage ligand for Rh/PPh_(3) system‐catalyzed homogeneous hydroformylation reactions.POC‐DICP not only displays enhanced hydroformylation selectivity(aldehyde selectivity as high as 97%and a linear‐to‐branch ratio as high as 1.89)but can also be recovered and reused via a simple precipitation method in homogeneous reaction systems.We speculate that the reason for the high activity and good selectivity is the favorable geometry(cone angle=123.88°)and electronic effect(P site is relatively electron‐deficient)of POC‐DICP,which were also demonstrated by density functional theory calculations and X‐ray absorption fine‐structure characterization.

Optimization of MgO/Al_2O_3 ratio for the maximization of active site densities in the Ni_2P/MgAlO catalysts for the hydrotreating reactions

The Ni2P/MgAlO catalysts with different MgO/Al2O3 ratios were prepared by the phosphidation of corresponding Ni/MgAlO catalysts with triphenylphosphine in liquid phase. It was found that the MgO/Al2O3 ratio affected the Ni2P/MgAlO catalysts significantly. The Ni2P/MgAlO catalyst with the MgO/Al2O3 ratio of 3 (w/w) exhibited the highly dispersed Ni2P particles (similar to 9 nm) with the highest CO uptake (344 mu mol/g) and thus the highest activities for the hydrotreating reactions. However, based on the CO uptakes on the used catalysts, the TOF values for the hydrodesulphurization of dibenzothiophene as well as those for the hydrogenation of tetralin on all the Ni2P/MgAlO catalysts were respectively similar, indicating that the MgO/Al2O3 ratio did not affect the intrinsic activities of Ni2P supported on the MgAlO support for the hydrotreating reactions. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

(31)~P NMR and ESI-MS Studies on Some Intermediates of the Peptide Coupling Reagents Triphenyl-chlorophosphoranes

The intermediates of the Appel coupling reagents were studied in acetonitrile, dimethoxyethane and dioxane by P NMR, C NMR spectrum and ESI-MS. In dioxane a new high 31 13 coordinated phosphorous compound with P NMR shift at -39 ppm was observed. The ESI-MS 31 showed that it could be a penta-coordinated phosphorous compound containing dioxane. The carboxyl activated intermediates were also studied in three solvents.

Synthesis and Crystal Structure of 2-(4’-Methylphenoxy)-5,8,9-trimethyl-3-phenyl Thieno[3′,2′:5,6]pyrido[4,3-d]pyrimidin-4-(3H)-one Hydrochloride

The title compound 2-（4＇-methylphenoxy）-5,8,9-trimethyl-3-phenyl thieno[3＇,2＇：5,6] pyrido[4,3-d]pyrimidin-4（3H）-one hydrochloride （C26H23Cl4N3O2S, Mr = 583.33） has been determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 14.8442（ 11 ）, b = 11.5131 （8）, c = 17.2010（13） A, β = 113.7250（10）°, V = 2691.3（3） ,A^3, Z = 4, Dc = 1.440 g/cm^3, S = 1.094,μ = 0.547 mm^-1, F（000） = 1200, the final R = 0.0571 and wR = 0.1458. X-ray analysis reveals that the title compound combines with a molecule of dichloromethane by an intramolecular hydrogen bond. The thienopyridine ring is almost coplanar, and the dihedral angle between the thiophene plane and the pyridine plane is 0.6°.

Synthesis and Structural Characterization of Organophosphorus Ylide-1-(3-nitrophenyl)-2-(triphenyl phosphoranylidene)ethanone

The title compound Ph3P=C（H）C（O）PhNO2 （L） has been prepared by the addition of triphenylphosphine in acetone as solvent to 2-bromo-1-（3,nitrophenyl）ethanone followed by the addition of alkaline solution of sodium hydroxide. The yellow crystals of the title ylide were grown in methanol/chloroform solution by drop method without stirring at room temperature. The solid state structure of ylide has been established by X-ray crystallography analysis. In the molecule of the title compound, the geometry around the P atom is nearly tetrahedral and the O atom is in synperiplanar orientation to the P atom. The nitrophenyl ring is twisted with respect to the plane of the carbonyl group through an angle of 36.6（1）°. The crystal （C26H20NO3P, Mr = 425.40） belongs to the monoclinic system, space group P21/n with a = 10.889（3）, b = 14.467（3）, e = 13.872（4）A, β = 103.08（3）°, V = 2128.6（10） A3, Z= 4, T= 100（2） K, R = 0.059 and wR = 0.163 for 3984 observed reflections with I〉 2σ（I）.