Phosphorodichloridates

The ether filtrate and washings were evaporated at room temperature under reduced pressure to give a clear liquid residue (801 grams). This residue was distilled under high vacuum to give trichloroethyl phosphorodichloridate (556 grams, 62.4% of theory), boiling point 75°C/0.8 mm. 

The phosphorodichloridate was hydrolyzed by adding to a stirred solution of sodium carbonate (253 grams) in water (2.9 liters). After 1 hour the solution was cooled and acidified with a solution of concentrated sulfuric acid (30 ml) in water (150 ml) and then extracted with a mixture of tetrahydrofuran and chloroform (2.3/1 3 x 1 liter). The tetrahydro-furan/chloroform liquors were bulked and evaporated to dryness to give a light brown oil. This was dissolved in water (1 liter) and titrated with 2N sodium hydroxide solution to a pH of 4.05 (volume required 930 ml). The aqueous solution was clarified by filtration through kieselguhr and then evaporated under reduced pressure to a syrup (737 grams). 

Phosphorylation of cholesterol followed by the normal hydrolytic work-up gives the phosphate monoester, not the symmetrical pyrophosphate diester as previously claimed. Cholesteryl phosphorodichloridate and some related steroidal phosphorodichloridates have been prepared from the action of pyrophosphoryl chloride on the appropriate alcohol ... 

Several of these steroid derivatives underwent elimination of phosphorodichloridate anion, giving hydrocarbon products, rather than ester formation when treated with methanolic pyridine. Pyrophosphoric acid itself has been used to phosphorylate (2-hydroxymethyl)pyridine. ... 

The reaction of /ra/w-l,2-dichloroethylene with phosphorus trichloride in the presence of oxygen has been shown to give the phosphorodichloridate (18), not the phosphonodichloridate (19) suggested previously. This reaction is almost certainly free-radical in character and possible chain mechanisms were proposed. 

Detailed interpretations of the n.m.r. spectra of vinylphosphonic acid," phosphoenolpyruvate, and some TV -phosphorylaziridines have been carried out. The vibrational spectra of ethyl phosphorodichloridate and its 1,1-dideuterio- and 2,2,2-trideuterio-derivatives have been examined. 

Imidocarbonyl Chloride Fluoride, Hydroxy-, Phosphorodibromidate Imidocarbonyl Chloride Fluoride, Hydroxy-, Phosphorodichloridate Imidocarbonyl Chloride, Hydroxy-, Methyl Phosphorochloridate Imidocarbonyl Chloride, Hydroxy-, Phosphorodichloridate Imidocarbonyl Fluoride, Hydroxy-, Ethyl Phosphorochloridate Imidocarbonyl Fluoride, Hydroxy-, Methyl Phosphorochloridate Imidocarbonyl Fluoride, Hydroxy-, Phosphorodichloridate Iminodiethanol Imochi Imochi-byo... 

The disadvantage of this method, especially for large-scale work, lies in the utilization of large quantities of pyridine. Furthermore, with ethyl alcohol some ethyl phosphorodichloridate (II) is usually produced even under conditions favourable to the production of diethyl phosphorochloridate. 

The reaction between benzoylhydrazine and ethyl or phenyl phosphorodichloridate yields 5-(2-benzoylhydrazino)-5,6-dihydro-2,8-diphenyl-4i7-l,3,4,6,7,5-oxatetra-azaphosphocine 5-oxide (32).87... 

G. B. Quistad, N. Zhang, S. E. Sparks, J. E. Casida, Phosphoacetylcholinesterase Toxicity of Phosphorus Oxychloride to Mammals and Insects That Can be Attributed to Selective Phosphorylation of Acetylcholinesterase by Phosphorodichloridic Acid , Chem. Res. Toxicol. 2000, 13, 652-657. 

C. Fuxyt S,N,N, S -tetramethytdiamidophoaphate. To 180 mL of dry diethyl ether, chilled to -30°C, is added 56.7 g (4.2 equiv) (1.26 mmol) of dimethylamine (Note 17). This solution is added during 1-2 hr from a double Jacketed dropping funnel, protected from moisture by a calcium chloride-tube and connected to a cryostat regulated to -30°C, to a stirred mixture (Note 18) of 60 g (0.30 mol) of the freshly distilled furyl phosphorodichloridate and 250 mL of ether in a two-necked, 1-L flask equipped with a condenser, protected from moisture by a calcium chloride-tube and connected to the cryostat. This flask is chilled in an ice bath during the addition of the first two equivalents of the dimethylamine. After the addition of... 

Furyl phosphorodichloridate Phosphorodichlorldic acid, 2-furany1 ester (12) (105262-70-2)... 

Compound Name Ethylhexaldehyde N-Propyl Alcohol Diethyl Carbonate Ethyl Chloracetate Ethyl Chloride Ethyl Chloroacetate Ethyl Chloroformate Ethyl Chloroacetate Ethyl Chloroacetate Ethyl Phosphorodichloridate Ethyldichlorosilane Ethylene... 

Ethyl Phosphorodichloridate Diethyl Phthalate Methylethylpyridine Ethyl Acrylate 2-Ethyl-3-Propylacrolein 2-Ethyl-3-Propylacrolein Tetraethyl Pyrophosphate Ethyl Silicate Ethyl Silicate Ethyl Silicate Ethyltrichlorosilane Ethyltrichlorosilane Ethyl Mercaptan... 

C2H6C14N2P2, Phosphorodichloridous hydraz-ide, 2-(dichlorophosphino)-1,2-dimethyl-, [37170-64-2], 32 133-34 C2H8B3N3, Borazine, 2-ethenyl-, [110272-04-3], 32 237-39... 

Chloroethanol Ethanol, 2-chloro- (107-07-3), 65,150 2-Chloroethyl dichlorophosphate Phosphorodichloridic acid, 2-chloroethyl ester (1455-05-6), 65, 68... 

Mol. wt. 298.64, m.p. 129-130°. The reagent is prepared by reaction of phenyl phosphorodichloridate with aniline in benzene. 

---