2001-45-8

Basic information

• Product Name: Tetraphenylphosphonium chloride
• Synonyms: TETRAPHENYLPHOSPHONIUM CHLORIDE;TETRAPHENYLPHOSPHONIUM CHLORID;Phosphonium, tetraphenyl-, chloride;Tetraphenylchlorophosphine;TETRAPHENYLPHOSPONIUM CHLORIDE;Tetraphenylphosphonium chloride, C 73.8%, H 5.5%;Tetraphenylphosphanium chloride;Tetraphenylphosphonium chloride,98%
• CAS NO: 2001-45-8
• Molecular Formula: C₂₄H₂₀P*Cl
• Molecular Weight: 374.84
• EINECS: 217-890-3
• Product Categories: Phosphonium Compounds;Greener Alternatives: Catalysis;Phase Transfer Catalysts;Phosphonium Salts;Liqiud crystal intermediates
• Mol File: 2001-45-8.mol
• Article Data: 11

Chemical Properties

• Melting Point: 272-274 °C(lit.)
• Boiling Point: °Cat760mmHg
• Flash Point: °C
• Appearance: White to beige/Crystalline Powder
• Density: g/cm³
• Storage Temp.: Inert atmosphere,Room Temperature
• Water Solubility: Soluble in water.
• Sensitive: Hygroscopic
• BRN: 3922393
• CAS DataBase Reference: Tetraphenylphosphonium chloride(CAS DataBase Reference)
• NIST Chemistry Reference: Tetraphenylphosphonium chloride(2001-45-8)
• EPA Substance Registry System: Tetraphenylphosphonium chloride(2001-45-8)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• F: 3-10
• Hazardous Substances Data: 2001-45-8(Hazardous Substances Data)

Usage

Chemical Properties

White to beige crystalline powder

Uses

Tetraphenylphosphonium chloride is used to generate lipophilic salts from inorganic and organometallic anions. Thus, Ph4P+ is useful as a phase-transfer catalyst, again because it allows inorganic anions to dissolve in organic solvents.

Preparation

Tetraphenylphosphonium chloride(PPh4Cl) and many analogous compounds can be prepared by the reaction of chlorobenzene with triphenylphosphine catalysed by nickel salts:PhCl + PPh3 → Ph4PCl

Application

Tetraphenylphosphonium chloride can be used to tune the crystallinity of CH3NH3PbI3 thin film during the deposition for boosting perovskite solar cells (PSCs) device performance. It can also be used as arylating reagents in Pd-catalyzed Heck reaction.

Reactions

Tetraphenylphosphonium chloride reacts with organometallic anionic complexes to give the corresponding salts. Depending on the size of the alkyl groups, the reaction of tetraphenylphosphonium chloride with a lithium dialkylamide can proceed in two directions to give 9-phenyl-9-phosphafluorene and benzene, or triphenylphosphine and the dialkylaniline. Lithium monoalkylamides react with tetraphenylphosphonium chloride to give (also depending on the size of the substituents) either N-alkyltriphenylphosphines or phosphine.

Purification Methods

Crystallise the chloride from acetone and dry at 70o under vacuum. It can also be recrystallised from a mixture of 1:1 or 1:2 dichloromethane/pet ether, the solvents having been dried over anhydrous K2CO3. The purified salt is dried at room temperature under a vacuum for 3days, and at 170o for a further 3days. Also recrystallise it from isoPrOH/Et2O or EtOH/Et2O. Extremely hygroscopic. [Wittig & Geissler Justus Liebigs Ann Chem 580 44, 50 1953, Willard et al. J Am Chem Soc 70 737 1948, Beilstein 16 III 851, 16 IV 984.]

InChI:InChI=1/C24H20P.ClH/c1-5-13-21(14-6-1)25(22-15-7-2-8-16-22,23-17-9-3-10-18-23)24-19-11-4-12-20-24;/h1-20H;1H/q+1;

Upstream product

• 591-51-5 phenyllithium 
• 791-28-6 Triphenylphosphine oxide 
• 108-90-7 chlorobenzene 
• 603-35-0 triphenylphosphine 
• 2588-88-7 pentaphenylphosphorane 
• 109-69-3 n-Butyl chloride 
• 4342-61-4 1,2-dichlorotetramethylsilane 
• 19171-57-4 dichlorotriphenyl-λ⁴-phosphane 
• 100-59-4 phenylmagnesium chloride 
• 2065-67-0 tetraphenylphosphonium iodide 
• 865-49-6 chloroform-d1 
• 1665-00-5 dichloromethane-d2 
• 75-09-2 dichloromethane 
• 63864-53-9 trans-[Pd(Ph)Cl(PPh₃)2] 

Downstream Products

• 98-10-2 benzenesulfonamide 
• 80563-09-3 Bis(tetraphenylphosphonium)-tris(phenylsulfonylimido)sulfit 
• 113679-99-5 bis(tetraphenylphosphonium) ethylenebis(dithiocarbamate) 
• 76711-99-4 Tetraphenylphosphonium-7-methoxy-1λ⁴,3λ²,5λ⁴,7λ⁴-tetrathia-2,4,6,8-tetraazabicyclo<3.3.0>octatrienid-3,3-dioxid 
• 83125-10-4 Tetraphenylphosphonium-bis(trifluormethylsulfonylimido)ethoxysulfinat 
• 87856-17-5 tetraphenyl-phosphonium; trichloride 
• 130101-71-2 tetraphenylphosphonium hexachloroarsenate 
• 29306-88-5 Tetraphenylphosphonium picrate 
• 146035-07-6 2-(2-Mercapto-ethylsulfanyl)-ethanethiolatetetraphenyl-phosphonium; 
• 49671-65-0 C₂₄H₂₀P⁽¹⁺⁾*C₆H₅Cl₄Te^(1-) 

Relevant articles and documents

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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.

Continuous synthesis method of tetraphenylphosphinophenylphenol salt

The method uses triphenylphosphine, halogenated benzene and phenol as raw materials, and the sodium hydroxide solution is an acid binding agent. The preparation method comprises the following steps: triphenylphosphine. The halogenated benzene and the reaction solvent are mixed in a continuous flow reactor to prepare a tetraphenylhalogenated phosphine solution, a prepared tetraphenylhalogenated phosphine solution, phenol and sodium hydroxide solution with a concentration 32% are mixed in a continuous flow reactor to prepare a tetraphenylphosphine phenol salt. Compared with a conventional stirred tank reactor, the reactor used in the preparation method is smaller in size, simple to operate, continuous in reaction, high in yield, environmentally friendly, stable in pH value during reaction, relatively mild in reaction conditions and stable in prepared tetraphenylphenol salt.

Long sought synthesis of quaternary phosphonium salts from phosphine oxides: Inverse reactivity approach

Quaternary phosphonium salts (QPS), a key class of organophosphorus compounds, have previously only been available by routes involving nucleophilic phosphorus. We report the realisation of the opposite approach to QPS utilising phosphine oxides as the electrophilic partner and Grignard reagents as nucleophiles. The process is enabled through the crucial intermediacy of the derived halophosphonium salts. The route does not suffer from the slow kinetics and limited availability of many parent phosphines and a broad range of QPS were prepared in excellent yields.