Diphenyl chlorophosphate

Description

Diphenyl chlorophosphate is a viscous colorless liquid. It can be prepared in situ by the reaction between diphenyl hydrogen phosphonate and carbon tetrachloride. It is used to prepare aromatic polyesters by polycondensation reaction in pyridine and polyesteramide. Diphenyl chlorophosphate is used as a phosphonating agent, such as to prepare phenylphosphonic acid.

Uses

Diphenyl chlorophosphate can be used to synthesize methadone, an opioid used for opioid maintenance therapy and for pain relief. It is used to control seedling grasses in turf. It undergoes anhydrous condensation with ethyl-4-bromo-butyrate and the hydrolysis product in alkaline medium of this condensation reaction is used in the quantitative determination of 3-cyano-3,3-diphenylpropionic acid.

Reference

1. F. Higashi, A. Hoshio, J. Kiyoshige, Preparation of aromatic polyesters by the direct polycondensation reaction with diphenyl chlorophosphate in pyridine, Polymer Chemistry, 1983, vol. 21, pp. 3241-3247
2. F. Higahi, M. Ozawa, A. Mochizuki, Synthesis of soluble aromatic polyesteramides by stepwise copolycondensation of bisphenols and aromatic diamines with diphenyl chlorophosphate in pyridine, 1986, vol. 24, pp.637-643
3. H. R. Allcock, M. A. Hofmann, C. M. Ambler, R. V. Morford, Phenylphosphonic Acid Functionalized Poly[aryloxyphosphazenes], 2002, vol. 35, pp. 3484-3489

Uses

Diphenyl chlorophosphate is used to prepare cyclohexyl-amidophosphoric acid diphenyl ester by reacting with cyclohexylamine. It is also used in the synthesis of alfa-substituted beta-lactams, anhydrides, esters and thioesters. It is also employed in the conversion of aldoximes to nitriles. Further, it is used in the preparation and reaction of enol phosphates, guanosine-adenosine-5',5'-triphosphate, guanosine-cytidine-5',5'-triphosphate, guanosine-uridine-5',5'-triphosphate, diguanosine-5',5'-diphosphate and diguanosine-5',5'-triphosphate. In addition to this, it serves as a phosphorylating agent for the preparation of 2-deoxy-D-galactose-3 and -6 phosphoric acids.

Uses

Diphenyl chlorophosphate may be used:

• in the preparation of guanosine-adenosine-5′,5′-triphosphate, guanosine-cytidine-5′,5′-triphosphate, guanosine-uridine-5′,5′-triphosphate, diguanosine-5′,5′-diphosphate and diguanosine-5′,5′-triphosphate
• as phosphorylating agent for the synthesis of 2-deoxy-D-galactose-3 and -6 phosphoric acids
• in the synthesis of diaryl phosphoryl derivatives of alkylene dithiophosphates

Preparation

The preparation of Diphenyl chlorophosphate is as follows:With a thermometer,Reflux condenser and mechanical agitation120 g of dichloromethane was placed in a 500 ml four-neck reaction flask.7.3 g of N,N-dimethylformamide,Stirring temperature control below 10 °C,Put 28g of bis(trichloromethyl) carbonate,A solution of 50 g of diphenyl phosphate and 120 g of dichloromethane was added.After the addition, the reaction was carried out for 3 hours. After the end of the reaction, the temperature was controlled below 10 ° C, 20 g of water was slowly added, and the mixture was stirred and the organic phase was dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the filtrate was evaporated under normal pressure. The temperature was lowered to 0 ° C, and the insoluble matter was removed by filtration to obtain 48.9 g of diphenyl chlorophosphate. The purity of GC was 99.2%, and the yield was 90.3%.

General Description

A clear colorless to light yellow liquid with a pungent odor. Insoluble in water and denser than water. Hence sinks in water. Contact may severely irritate skin, eyes and mucous membranes. Flash point above 235°F.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Diphenyl chlorophosphate is incompatible with bases (including amines) strong oxidizing agents, and alcohols. May react vigorously or explosively if mixed with diisopropyl ether or other ethers in the presence of trace amounts of metal salts [J. Haz. Mat., 1981, 4, 291]. May form highly toxic and flammable phosphine gas in the presence of strong reducing agents such as hydrides. Partial oxidation by oxidizing agents may result in the release of toxic phosphorus oxides.

Health Hazard

TOXIC; inhalation, ingestion or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

Fire Hazard

Non-combustible, substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic fumes. Some are oxidizers and may ignite combustibles (wood, paper, oil, clothing, etc.). Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated.

Synthesis

108-95-2

2524-64-3

To a 1000 liter reactor 376 kg of phenol, 323 kg of phosphorous trichloride and distilled substrate were sequentially added, stirring was turned on and the reaction system was heated. The temperature was slowly increased to 140 °C over a period of 4 h. The reaction was maintained at this temperature. The progress of the reaction was monitored by gas chromatography (GC) until the phenol content dropped below 0.5%. Upon completion of the reaction, the reaction solution was transferred to a distillation column for decompression distillation, and the fraction with a boiling point of 150 ± 2 °C/4 mmHg was collected to give 475 kg of finished diphenyl chlorophosphate. The process yield was 88.6% and the GC purity was 99.3%.

Purification Methods

Fractionally distil it in 30 351.5490. a good vacuum; better use a spinning band column. [Walsh J Am Chem Soc 81 3023 1959, IR: Bellamy & Beecher J Chem Soc 475 1952, Beilstein 6 IV 737.]

References

[1] Patent: CN106810575, 2017, A. Location in patent: Paragraph 0014
[2] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1985, vol. 34, # 4, p. 799 - 802
[3] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1985, # 4, p. 878 - 882
[4] Journal of Organic Chemistry, 1992, vol. 57, # 23, p. 6294 - 6300
[5] Chemische Berichte, 1939, vol. 72, p. 2121,2127