6224-63-1

Basic information

• Product Name: TRI-M-TOLYLPHOSPHINE
• Synonyms: Tri-m-tolyphosphine;Tris(m-tolyl)phosphine, 98+%;Tri(m-tolyl)phosphine,98+%;TRIS(M-TOLYL)PHOSPHINE (TMTP);Tris(m-methylphenyl)phosphine;tris(3-Methylphenyl)phosphane;Phosphine,tris(3-Methylphenyl)-;Tri-M-tolylphosphin
• CAS NO: 6224-63-1
• Molecular Formula: C₂₁H₂₁P
• Molecular Weight: 304.37
• EINECS: 228-312-4
• Product Categories: Ligand;Phosphine Ligands;Synthetic Organic Chemistry;Basic Phosphine LigandsCatalysis and Inorganic Chemistry;Catalysis and Inorganic Chemistry;Cross-Coupling;Phosphine Ligands;Phosphorus Compounds;organophosphorus ligand;Achiral Phosphine;Aryl Phosphine
• Mol File: 6224-63-1.mol

Chemical Properties

• Melting Point: 97-99 °C(lit.)
• Boiling Point: 423.1 °C at 760 mmHg
• Flash Point: 221.6 °C
• Appearance: white/crystal
• Vapor Pressure: 5.65E-07mmHg at 25°C
• Storage Temp.: Inert atmosphere,Room Temperature
• Water Solubility: Insoluble in water.
• Sensitive: Air Sensitive
• BRN: 658863
• CAS DataBase Reference: TRI-M-TOLYLPHOSPHINE(CAS DataBase Reference)
• NIST Chemistry Reference: TRI-M-TOLYLPHOSPHINE(6224-63-1)
• EPA Substance Registry System: TRI-M-TOLYLPHOSPHINE(6224-63-1)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38-38-37-36
• Safety Statements: 26-36
• WGK Germany: 3
• F: 10-23
• TSCA: Yes
• Hazardous Substances Data: 6224-63-1(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
Tri-m-tolylphosphine is used as a reagent in the Suzuki reaction, a widely employed method for the formation of carbon-carbon bonds, particularly in the synthesis of biaryl compounds. Its ability to facilitate cross-coupling reactions makes it a valuable component in the field of organic chemistry.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, Tri-m-tolylphosphine is used for the preparation of various drugs and active pharmaceutical ingredients. Its role in the synthesis of complex molecules contributes to the development of new medications with improved efficacy and reduced side effects.
Used in Crystal Structure Analysis:
Tri-m-tolylphosphine is utilized as a reagent in the determination of crystal structures, providing valuable insights into the arrangement of atoms and molecules in solid-state materials. This information is crucial for understanding the properties and behavior of compounds, which can be applied in the design of new materials and drugs.
Used in Multinuclear NMR:
In the field of nuclear magnetic resonance (NMR) spectroscopy, Tri-m-tolylphosphine is employed as a reagent for multinuclear NMR studies. This technique allows for the investigation of various elements within a molecule, providing detailed information about its structure and dynamics.
Used in Antitumor Activity Research:
Tri-m-tolylphosphine has been found to exhibit antitumor activity, making it a potential candidate for the development of new cancer treatments. Its ability to target and disrupt specific cellular processes in cancer cells offers hope for the creation of more effective therapies.
Used in Photolysis of Silver Methylxanthate Complexes:
In the study of photolysis of silver methylxanthate complexes, Tri-m-tolylphosphine is used to investigate the interactions between these complexes and human adrenocarcinoma breast cancer cells. This research contributes to the understanding of the mechanisms underlying the antitumor effects of these complexes and may lead to the development of novel cancer treatments.

InChI:InChI=1/C21H21P/c1-16-7-4-10-19(13-16)22(20-11-5-8-17(2)14-20)21-12-6-9-18(3)15-21/h4-15H,1-3H3

Upstream product

• 28987-79-3 m-tolylmagnesium bromide 
• 108-41-8 1-chloro-3-methylbenzene 
• 591-17-3 meta-bromotoluene 
• 373623-33-7 m-tolylzinc(II) bromide 
• 119821-88-4 (2-quinaldinate)(carbonyl)(P(3-CH₃-C₅H₄)3)2rhodium(I) 
• 119821-88-4 (2-quinaldinate)(carbonyl)(P(3-CH₃-C₅H₄)3)2rhodium(I) 
• 6151-88-8 tri(m-tolyl)phosphine oxide 
• 352-70-5 m-Fluorotoluene 
• 352-32-9 p-fluorotoluene 
• 625-95-6 3-Iodotoluene 

Downstream Products

• 6151-88-8 tri(m-tolyl)phosphine oxide 
• 14796-90-8 N-Phenylimino-tris--phosphoran 
• 126742-75-4 C₂₁H₂₁OP*C₇H₉NO₂S 
• 73116-98-0 4,4,5,5-Tetramethyl-2,2,2-tri-m-tolyl-2λ⁵-[1,3,2]dioxaphospholane 
• 6163-62-8 tri(3-methylphenyl)phosphine sulfide 
• 882-33-7 diphenyldisulfane 
• 10061-85-5 tri(3-methylphenyl)phosphine selenide 
• 10177-78-3 di-(3-methylphenyl)-phosphine 
• 142733-55-9 Tris-(3-methyl-cyclohexyl)-phosphane 
• 7293-71-2 Tris--fluorenyl-(9)-phosphoniumbromid 
• 3474-41-7 m-tolyl 
• 7293-82-5 Tris--phosphonium-9-fluorenylid 
• 204761-54-6 [(η5-C5H5)Ru(P(3-CH3-C6H4)3)2Cl] 
• 72868-13-4 (CO)3NiP(C₆H₄CH₃-m)3 

Relevant articles and documents

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.

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.

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.

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.

Superbase-Assisted Selective Synthesis of Triarylphosphines from Aryl Halides and Red Phosphorus: Three Consecutive Different SNAr Reactions in One Pot

Aryl halides, ArX (Ar = Ph, 2-, 3- and 4-Tol, 1- and 2-Np, 4-C6H4CONH2; X = F, Cl, Br), rapidly and exothermically (100–180 °C, 0.5–2 h) react with red phosphorus in superbase systems KOH/L, where L is a polar nonhydroxylic complexing solvent (ligand), such as NMP, DMSO, HMPA, to afford the corresponding triarylphosphines (Ar3P) in up to 74 % yield (for X = F). Thus, three consecutive reactions of SNAr (aromatic nucleophilic substitution) to form the three C(sp2)–P bonds are realized in one pot. The synthesis is mostly chemoselective (with rare exception): neither mono- nor diphosphines have been isolated. The best results were attained when aryl fluorides were treated with red phosphorus (Pn) in the KOH/NMP superbase system. This environmentally friendly, PCl3-free synthesis of Ar3P from available starting materials opens an easy and straightforward access to triarylphosphines, which are important ligands, synthetic auxiliaries, and components of high-tech- and medicinally oriented complexes.

Electrophilic Phosphonium Cation-Mediated Phosphane Oxide Reduction Using Oxalyl Chloride and Hydrogen

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 %).

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.

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.

Electroreduction of tetra-coordinate phosphonium derivatives; One-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al3+, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.

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.