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| Names | |
|---|---|
| IUPAC name Phosphorus trichloride | |
| Systematic IUPAC name Trichlorophosphane | |
| Other names Phosphorus(III) chloride Phosphorous chloride | |
| Identifiers | |
3D model (JSmol) | |
| ChEBI | |
| ChemSpider |
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| ECHA InfoCard | 100.028.864  |
| EC Number |
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PubChem CID | |
| RTECS number |
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| UNII | |
| UN number | 1809 |
CompTox Dashboard (EPA) | |
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| Properties | |
| PCl3 | |
| Molar mass | 137.33 g/mol |
| Appearance | Colorless to yellow fuming liquid[1] |
| Odor | unpleasant, acrid, like hydrochloric acid[1] |
| Density | 1.574 g/cm3 |
| Melting point | −93.6 °C (−136.5 °F; 179.6 K) |
| Boiling point | 76.1 °C (169.0 °F; 349.2 K) |
| hydrolyzes | |
| Solubility in other solvents | soluble[vague] in benzene, CS2, ether, chloroform, CCl4, halogenated organic solvents reacts with ethanol |
| Vapor pressure | 13.3 kPa |
| −63.4·10−6 cm3/mol | |
Refractive index (nD) | 1.5122 (21 °C) |
| Viscosity | 0.65 cP (0 °C) 0.438 cP (50 °C) |
| 0.97 D | |
| Thermochemistry | |
Std enthalpy of formation (ΔfH⦵298) | −319.7 kJ/mol |
| Hazards | |
| Occupational safety and health (OHS/OSH): | |
Main hazards | Highly toxic,[2] corrosive |
| GHS labelling:[4] | |
   | |
| Danger | |
| H300, H301, H314, H330, H373 | |
| P260, P273, P284, P303+P361+P353, P304+P340+P310, P305+P351+P338 | |
| NFPA 704 (fire diamond) | |
| Lethal dose or concentration (LD, LC): | |
LD50 (median dose) | 18 mg/kg (rat, oral)[3] |
LC50 (median concentration) | 104 ppm (rat, 4 hr) 50 ppm (guinea pig, 4 hr)[3] |
| NIOSH (US health exposure limits): | |
PEL (Permissible) | TWA 0.5 ppm (3 mg/m3)[1] |
REL (Recommended) | TWA 0.2 ppm (1.5 mg/m3) ST 0.5 ppm (3 mg/m3)[1] |
IDLH (Immediate danger) | 25 ppm[1] |
| Safety data sheet (SDS) | ICSC 0696 |
| Related compounds | |
Related phosphorus chlorides | Phosphorus pentachloride Phosphorus oxychloride Diphosphorus tetrachloride |
Related compounds | Phosphorus trifluoride Phosphorus tribromide Phosphorus triiodide |
| Supplementary data page | |
| Phosphorus trichloride (data page) | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.
Phosphorus trichloride was first prepared in 1808 by the French chemists Joseph Louis Gay-Lussac and Louis Jacques Thénard by heating calomel (Hg2Cl2) with phosphorus.[5] Later during the same year, the English chemist Humphry Davy produced phosphorus trichloride by burning phosphorus in chlorine gas.[6]
World production exceeds one-third of a million tonnes.[7] Phosphorus trichloride is prepared industrially by the reaction of chlorine with white phosphorus, using phosphorus trichloride as the solvent. In this continuous process PCl3 is removed as it is formed in order to avoid the formation of PCl5.
It has a trigonal pyramidal shape. Its 31P NMR spectrum exhibits a singlet around +220 ppm with reference to a phosphoric acid standard.[citation needed]
The phosphorus in PCl3 is often considered to have the +3 oxidation state and the chlorine atoms are considered to be in the −1 oxidation state. Most of its reactivity is consistent with this description.[8]
PCl3 is a precursor to other phosphorus compounds, undergoing oxidation to phosphorus pentachloride (PCl5), thiophosphoryl chloride (PSCl3), or phosphorus oxychloride (POCl3).
PCl3 reacts vigorously with water to form phosphorous acid (H3PO3) and hydrochloric acid:
Phosphorus trichloride is the precursor to organophosphorus compounds. It reacts with phenol to give triphenyl phosphite:
Alcohols such as ethanol react similarly in the presence of a base such as a tertiary amine:[9]
With one equivalent of alcohol and in the absence of base, the first product is alkoxyphosphorodichloridite:[10]
In the absence of base, however, with excess alcohol, phosphorus trichloride converts to diethylphosphite:[11][12]
Secondary amines (R2NH) form aminophosphines. For example, bis(diethylamino)chlorophosphine, (Et2N)2PCl, is obtained from diethylamine and PCl3. Thiols (RSH) form P(SR)3. An industrially relevant reaction of PCl3 with amines is phosphonomethylation, which employs formaldehyde:
The herbicide glyphosate is also produced this way.
The reaction of PCl3 with Grignard reagents and organolithium reagents is a useful method for the preparation of organic phosphines with the formula R3P (sometimes called phosphanes) such as triphenylphosphine, Ph3P.
Triphenylphosphine is produced industrially by the reaction between phosphorus trichlorid, chlorobenzene, and sodium:[13]
Under controlled conditions or especially with bulky R groups, similar reactions afford less substituted derivatives such as chlorodiisopropylphosphine.
Phosphorus trichloride is commonly used to convert primary and secondary alcohols to the corresponding chlorides.[14] As discussed above, the reaction of alcohols with phosphorus trichloride is sensitive to conditions. The mechanism for the ROH →RCl conversion involves the reaction of HCl with phosphite esters:
The first step proceeds with nearly ideal stereochemistry but the final step far less so owing to an SN2 pathway.
Phosphorus trichloride undergoes a variety of redox reactions:[13]
Phosphorus trichloride has a lone pair, and therefore can act as a Lewis base,[15] e.g., forming a 1:1 adduct Br3B-PCl3. Metal complexes such as Ni(PCl3)4 are known, again demonstrating the ligand properties of PCl3.
This Lewis basicity is exploited in the Kinnear–Perren reaction to prepare alkylphosphonyl dichlorides (RP(O)Cl2) and alkylphosphonate esters (RP(O)(OR')2). Alkylation of phosphorus trichloride is effected in the presence of aluminium trichloride give the alkyltrichlorophosphonium salts, which are versatile intermediates:[16]
The RPCl+
3 product can then be decomposed with water to produce an alkylphosphonic dichloride RP(=O)Cl2.
PCl3, like the more popular phosphorus trifluoride, is a ligand in coordination chemistry. One example is Mo(CO)5PCl3.[17]
PCl3 is important indirectly as a precursor to PCl5, POCl3 and PSCl3, which are used in many applications, including herbicides, insecticides, plasticisers, oil additives, and flame retardants.
For example, oxidation of PCl3 gives POCl3, which is used for the manufacture of triphenyl phosphate and tricresyl phosphate, which find application as flame retardants and plasticisers for PVC. They are also used to make insecticides such as diazinon. Phosphonates include the herbicide glyphosate.
PCl3 is the precursor to triphenylphosphine for the Wittig reaction, and phosphite esters which may be used as industrial intermediates, or used in the Horner-Wadsworth-Emmons reaction, both important methods for making alkenes. It can be used to make trioctylphosphine oxide (TOPO), used as an extraction agent, although TOPO is usually made via the corresponding phosphine.
PCl3 is also used directly as a reagent in organic synthesis. It is used to convert primary and secondary alcohols into alkyl chlorides, or carboxylic acids into acyl chlorides, although thionyl chloride generally gives better yields than PCl3.[18]
Industrial production of phosphorus trichloride is controlled under the Chemical Weapons Convention, where it is listed in schedule 3, as it can be used to produce mustard agents.[23]
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