4895-65-2

Basic information

• Product Name: Phenyltetrachlorphosphorus
• Synonyms: Phenyltetrachlorphosphorus;Tetrachloro(phenyl)phosphorane;Phenylphosphorus tetrachloride;Phosphorane, tetrachlorophenyl- (6CI,7CI,8CI,9CI)
• CAS NO: 4895-65-2
• Molecular Formula: C₆H₅Cl₄P
• Molecular Weight: 249.89
• Mol File: 4895-65-2.mol
• Article Data: 9

Chemical Properties

• Appearance: /
• CAS DataBase Reference: Phenyltetrachlorphosphorus(CAS DataBase Reference)
• NIST Chemistry Reference: Phenyltetrachlorphosphorus(4895-65-2)
• EPA Substance Registry System: Phenyltetrachlorphosphorus(4895-65-2)

Safety Data

• Hazardous Substances Data: 4895-65-2(Hazardous Substances Data)

Usage

General Description

Phenyltetrachlorphosphorus is a chemical compound that consists of a phenyl group attached to four chlorine atoms and one phosphorus atom. It is a highly reactive and toxic compound that is used primarily as a building block for the synthesis of various organophosphorus compounds. Phenyltetrachlorphosphorus is also used as a catalyst in some organic reactions. Due to its toxic nature, it is handled with extreme care in laboratory settings and industrial processes. Additionally, it is important to note that exposure to phenyltetrachlorphosphorus can result in adverse health effects, including irritation to the skin, eyes, and respiratory system, and potentially more serious systemic effects if not properly handled.

InChI:InChI=1/C6H5Cl4P/c7-11(8,9,10)6-4-2-1-3-5-6/h1-5H

Synthetic route

Dichlorophenylphosphine (644-97-3) → phenyltetrachlorophosphorane (4895-65-2)

Conditions	Yield
With chlorine In tetrachloromethane at 20℃; for 5h;	86%
With chlorine
With chlorine In benzene octane was used as well (as solvent);
With chlorine In chloroform at 30℃; for 0.333333h;

Dichlorophenylphosphine (644-97-3) → phenyltetrachlorophosphorane (4895-65-2) + phenylthiophosphonic acid dichloride (3497-00-5)

Conditions	Yield
With sulphur monochloride

P,P-dichlorophenylphosphine oxide (824-72-6) → phenyltetrachlorophosphorane (4895-65-2)

Conditions	Yield
With chlorine

phenyltrichlorophosphonium hexachlorophosphorate (55045-25-5) → 3-chloro-cyclohexene (2441-97-6) + phenyltetrachlorophosphorane (4895-65-2) + trans-1,2-dichlorocyclohexane (822-86-6)

Conditions	Yield
With cyclohexene In 1,2-dichloro-ethane at 60℃; for 2h; Yields of byproduct given. Title compound not separated from byproducts;

phenyltrichlorophosphonium hexachlorophosphorate (55045-25-5) → phenyltetrachlorophosphorane (4895-65-2)

Conditions	Yield
With cyclohexene In 1,2-dichloro-ethane at 60℃; for 2h; Mechanism;

triphenylphosphine (603-35-0) → phenyltetrachlorophosphorane (4895-65-2)

Conditions	Yield
With chlorine In toluene

cyclohexene (110-83-8) → 3-chloro-cyclohexene (2441-97-6) + phenyltetrachlorophosphorane (4895-65-2) + trans-1,2-dichlorocyclohexane (822-86-6)

Conditions	Yield
With phenyltrichlorophosphonium hexachlorophosphorate In 1,2-dichloro-ethane at 60℃; for 2h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

chlorine (7782-50-5) + Dichlorophenylphosphine (644-97-3) → phenyltetrachlorophosphorane (4895-65-2)

Iodine monochloride (7790-99-0) + Dichlorophenylphosphine (644-97-3) → phenyltetrachlorophosphorane (4895-65-2)

diphenylmercury(II) (587-85-9) → phenyltetrachlorophosphorane (4895-65-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: phosphorus trichloride / 180 °C 2: chlorine View Scheme

benzene (71-43-2) → phenyltetrachlorophosphorane (4895-65-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: phosphorus trichloride 2: chlorine View Scheme

P,P-dichlorophenylphosphine oxide (824-72-6) + nicotinic acid (59-67-6) + Dichlorophenylphosphine (644-97-3) → phenyltetrachlorophosphorane (4895-65-2)

Conditions	Yield
With chlorine

phenyltetrachlorophosphorane (4895-65-2) → P,P-dichlorophenylphosphine oxide (824-72-6)

Conditions	Yield
With sodium dithionite In tetrachloromethane at 20℃; Substitution;	96%
With water
With sulfur dioxide
Multi-step reaction with 2 steps 1: NEt3 / CH2Cl2 / 13 h / 40 °C 2: 38 percent Spectr. / NEt3 / toluene; CH2Cl2 / 4 h / 0 °C View Scheme
With amino acid at 20 - 25℃;

2,6-diimino-3,3,4,4,5,5-hexafluoropiperidine (376-67-0) + phenyltetrachlorophosphorane (4895-65-2) → 2,2,6-trichloro-3,3,4,4,5,5-hexafluoro-2,3,4,5-tetrahydropyridine (714-36-3)

Conditions	Yield
reflux, 15 h;; byproducts are easy to remove;;	95%
reflux, 15 h;; byproducts are easy to remove;;	95%

phenyltetrachlorophosphorane (4895-65-2) → phenyltetraiodophosphorane (26852-27-7)

Conditions	Yield
With trimethylsilyl iodide In benzene at 20℃; for 1h;	91%

phenyltetrachlorophosphorane (4895-65-2) + ethyl vinyl ether (109-92-2) → trichloro(2-ethoxyvinyl)phenylphosphorane (90876-60-1)

Conditions	Yield
In tetrachloromethane at 60℃; for 0.5h;	87%

phenyltetrachlorophosphorane (4895-65-2) → Dichlorophenylphosphine (644-97-3)

Conditions	Yield
With tetraethylammonium iodide In benzene for 1h;	79%
With phosphorous acid trimethyl ester; triethyl phosphite

phenyltetrachlorophosphorane (4895-65-2) + 3-trifluoromethylaniline (98-16-8) → C13H9Cl2F3NP (76616-13-2)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	78%

phenyltetrachlorophosphorane (4895-65-2) + 3-amino-4-chlorobenzotrifluoride (121-50-6) → C13H8Cl3F3NP (76616-20-1)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	71%

trimethylsilyl cyanide (7677-24-9) + phenyltetrachlorophosphorane (4895-65-2) → ethanedinitrile (460-19-5) + dicyano(phenyl)phosphine (2946-59-0)

Conditions	Yield
In tetrachloromethane for 0.25h;	A n/a B 70%

2-(1,1,2,2-tetrafluoroethoxy)aniline (35295-34-2) + phenyltetrachlorophosphorane (4895-65-2) → C14H10Cl2F4NOP (76616-14-3)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	63%

4-chloro-2-(trifluoromethyl)aniline (445-03-4) + phenyltetrachlorophosphorane (4895-65-2) → C13H8Cl3F3NP (76616-18-7)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	63%

3-(1,1,2,2-tetrafluoroethoxy)aniline (831-75-4) + phenyltetrachlorophosphorane (4895-65-2) → C14H10Cl2F4NOP (76616-15-4)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	62%

phenyltetrachlorophosphorane (4895-65-2) + ethyl vinyl ether (109-92-2) → P,P-dichlorophenylphosphine oxide (824-72-6) + phenyl-β-ethoxyvinylphosphinic chloride (90876-11-2)

Conditions	Yield
With acetone In benzene 2.) 5 deg C;	A 20% B 58%

-butyl vinyl ether (111-34-2) + phenyltetrachlorophosphorane (4895-65-2) → phenyl-β-chlorovinylphosphinic chloride (3135-58-8)

Conditions	Yield
In benzene for 24h;	57%

phenyltetrachlorophosphorane (4895-65-2) + 2,2,2-trifluoro-N,N'-dimethylacetamidine (86650-37-5) → 1,3-dimethyl-2,2-dichloro-2-phenyl-4-chloro-4-(trifluoromethyl)-1,3,2-diazaphosphetidine

Conditions	Yield
In benzene at 0℃; for 12h;	56%

2,4-difluorophenylamine (367-25-9) + phenyltetrachlorophosphorane (4895-65-2) → C12H8Cl2F2NP (76616-16-5)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	54%

phenyltetrachlorophosphorane (4895-65-2) + 2-(trifluoromethyl)benzenamine (88-17-5) → C13H9Cl2F3NP (76616-12-1)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	46%

phenyltetrachlorophosphorane (4895-65-2) + sodium 1-trifluoromethyl-2-cyano-2-trifluoromethylthiovinyl oxide → 1-cyano-1-trifluoromethylthio-2-chloro-2-trifluoromethylethylene (77429-05-1)

Conditions	Yield
In dichloromethane	42.3%
In dichloromethane	42.3%

phenyltetrachlorophosphorane (4895-65-2) + 3,3,3-trichloro-2-<(trimethylsilyl)imino>propionitrile (71985-40-5) → P-phenyl-N-(1,2,2,2-tetrachloro-1-cyanoethyl)phosphonimidic dichloride (76486-56-1)

Conditions	Yield
In tetrachloromethane for 16h; Heating;	40%

3-chloro-4-fluorophenylamine (367-21-5) + phenyltetrachlorophosphorane (4895-65-2) → C12H8Cl3FNP (76616-17-6)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	38%

phenyltetrachlorophosphorane (4895-65-2) + 4-chloro-3-trifluoromethyl-aniline (320-51-4) → C13H8Cl3F3NP (76616-19-8)

Conditions	Yield
In 1,2-dichloro-ethane Heating;	31%

diazomethane (186581-53-3, 908094-01-9) + phenyltetrachlorophosphorane (4895-65-2) → phenylbis(chloromethyl)phosphine oxide (18788-46-0)

Conditions	Yield
beim Behandeln anschliessend mit H2O;
bei nachfolgenden Umsetzung mit H2O;

benzenesulfonamide (98-10-2) + phenyltetrachlorophosphorane (4895-65-2) → P-phenyl-N-(phenylsulfonyl)phosphonimidic dichloride (52315-49-8)

phenylphosphonate (1571-33-1) + phenyltetrachlorophosphorane (4895-65-2) → P,P-dichlorophenylphosphine oxide (824-72-6)

phenyltetrachlorophosphorane (4895-65-2) → phenylphosphonate (1571-33-1)

Conditions	Yield
With water

phenyltetrachlorophosphorane (4895-65-2) → phenyltetrafluorophosphorane (666-23-9)

Conditions	Yield
With antimony(III) fluoride

phenyltetrachlorophosphorane (4895-65-2) → ethyl hydrogen phenylphosphonate (4546-19-4)

Conditions	Yield
With ethanol

phenyltetrachlorophosphorane (4895-65-2) → 6-chloro-2,4,6-triphenyl-2λ5,4λ5,6λ5-cyclotriphosphazene-2,4-diol

Conditions	Yield
With ammonium chloride; 1,1,2,2-tetrachloroethane at 140℃; und Erhitzen des Reaktionsprodukts mit Essigsaeure;

phenyltetrachlorophosphorane (4895-65-2) + acetic acid (64-19-7) → P,P-dichlorophenylphosphine oxide (824-72-6) + acetyl chloride (75-36-5)

phenyltetrachlorophosphorane (4895-65-2) + 4-chloro-phenol (106-48-9) → phenyl-phosphonic acid bis-(4-chloro-phenyl ester) (20858-29-1)

Upstream product

• 824-72-6 P,P-dichlorophenylphosphine oxide 
• 59-67-6 nicotinic acid 
• 644-97-3 Dichlorophenylphosphine 
• 71-43-2 benzene 
• 587-85-9 diphenylmercury(II) 
• 7790-99-0 Iodine monochloride 
• 7782-50-5 chlorine 
• 110-83-8 cyclohexene 
• 603-35-0 triphenylphosphine 
• 55045-25-5 phenyltrichlorophosphonium hexachlorophosphorate 

Downstream Products

• 824-72-6 P,P-dichlorophenylphosphine oxide 
• 75-36-5 acetyl chloride 
• 4762-50-9 anilinium phenylphosphonate 
• 14360-83-9 tetraphenyl-cyclodiphosphazane-2,4-dioxide 
• 861378-75-8 (3-ethoxycarbonylamino-phenyl)-phosphonic acid 
• 94685-67-3 bis(4-methylphenylamino)phenylphosphine oxide 
• 5427-30-5 m-aminophenylphosphonic acid 
• 94312-82-0 phenyl-phosphonic acid anilide-p-toluidide 
• 107422-60-6 phenyl-piperidino-phosphinic acid anilide 
• 5337-19-9 (m-nitrophenyl)phosphonic acid 
• 3049-24-9 diphenyl phenylphosphonate 
• 2310-87-4 phenyl-phosphonic acid monophenyl ester 
• 1142-49-0 phenyl-phosphonic acid-monofluoride; compound with aniline 
• 69571-53-5 bis(iodomethyl)(phenyl)phosphine oxide 

Relevant articles and documents

Ionic-Molecular Isomerism in Chlorophenylphosphoranes PhnPCl5-n (1n3)

Both ionic and molecular modifications of the three chlorophenylphosphoranes PhnPCl5-n (1n3) have been isolated for the first time as solids and all have been characterised by elemental analysis, Raman spectroscopy and 31P magic angle spinning (MAS) NMR spectroscopy.

Preparation of aryl halides

A process for selectively substituting an aromatic nitro group with a halo group which comprises contacting the nitroaromatic compound with a phosphorushalide of formula: Rn PX5-n wherein n is selected from 0, 1, 2 and 3; R is selected from the group consisting of C-6 to C-10 aryl and substituted aryl wherein the substituents are selected from the group consisting of: straight and branched chain alkyl, alkoxy, and haloalkyl; halogen, sulfonate and mixtures thereof; and X is a halogen in the presence of an arylphosphorusoxydihalide solvent. The use of an arylphosphorustetrahalide and particularly phenylphosphorustetrachloride is preferred. The arylphosphorustetrahalide can be prepared in situ by contacting a solution of the corresponding arylphosphorusdihalide in an arylphosphorusoxydihalide solvent with a halogen. The process can further comprise the step of heating the reaction mixture to maintain a temperature of from about 100° C. to about 175° C. for from about 1 hour to about 24 hours.