Phosphorochloridates diethyl phosphorochloridate

Diethyl chlorophosphate Phosphorochloridic acid, diethyl ester (3,9) (814-49-3)... 

Difluoroalkylphosphonates, prepared from difluoroaliylic allcoxides and diethyl phosphorochloridate, are remarkably stable [78] (equation 65). 

Water hydrolyzes diethyl phosphorochloridate [chloro-diethoxyphosphorus(V) oxide] readily but does not affect the diene. Alternatively, the reaction mixture can be processed by fractionation. Evaporation of the petroleum ether and fractionation of the residue through a 25-cm. x 2.2-cm. column of glass helices yields 170 g. (98.5%) of diethyl phosphorochloridate, b.p. 34-36°/0.2 mm., d 1.4210-1.4250 (the refractive index indicates that it contains 5-10% of the title compound), and 240-255 g. (90-96%) of l,2,3,4,5-pentachloro-5-ethylcyclo-pentadiene, b.p. 51-53°/0.2 mm., 1.5398. 

The reaction mixture can also be processed by chromatography. The crude reaction mixture is poured on a 90-cm. x 4.5-cm. column of alumina (e.g, Fisher adsorption grade ) and eluted with about 2 1. of technical-grade pentane. This yields a pale-yellow solution that is free of diethyl phosphorochloridate. Evaporation of the pentane gives 240-255 g. (90-96%) of l,2,3,4,5-pentachloro-5-ethylcyclopentadiene. 

Preparation of diethyl 3-trifluoromethylphenylphosphonate — Reaction of a Grignard reagent with a dialkyl phosphorochloridate... 

The ester/alkyne rearrangement system can be extended by conjugation to involve a more distant site. The reaction of diethyl phosphorochloridate with 3-methylhex-4-yne-2-ene-l-ol leads to the vinylogous propargylic ester rearrangement as shown in Equation 4.39.176... 

Diethyl malonate, condensation with acetone, 50, 39 Diethyl 5-methylcoprost-3-en-yl phosphate, 52, 109 Diethyl phosphorochloridate,... 

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 diethyl phosphorochloridate was characterized by the Ciystalline diethyl phenylphosphoramidate (VI) formed by the action of aniline. 

Dimethyl and diethyl phosphorofluoridate were hydrolysed much more quickly, the order being Me>Et>Pr complete hydrolysis of the ethyl ester took about 4 hr. Small quantities of the di-isopropyl, but not the diethyl ester, could be steam-distilled. Bi-isopropyl phosphorochloridate can be readily identified by allowing it to react with aniline to give the crystalline phenylphosphoramidate ... 

Gaseous ammonia reacted with the phosphorochloridate at 0° producing solid diethyl phosphoramidate in accordance with the equation Et,PO,a+2NH, = Et POjNH4+NH C1. 

The 2-chloroethyl group, which is often an effective toxo-phore, was then attached to phosphorus through oxygen. No reaction appeared to take place between ethylene chlorohydrin and diethyl phosphorochloridate in the absence of a tertiary base. In the presence of pyridine, however, which removed the hydrogen chloride formed, a smooth reaction took place at 0° with the formation of diethyl 2-chloroethyl phosphate,... 

We obtained diethyl phosphorocyanidate (V) in only small yield by the action of potassium cyanide on the corresponding phosphorochloridate. We were able to prepare it,6 however, by the action of cyanogen iodide on the phosphite. This is apparently a modified Arbusov reaction ... 

Tetraethyl pyrophosphate (T.E.P.P.) was prepared by Toy1 in 73 per cent yield by the controlled hydrolysis of diethyl phosphorochloridate in the presence of a tertiary base ... 

Kosolapoff2 has prepared T.E.P.P. by the action of chlorine on a mixture of sodium diethyl phosphate and diethyl phosphorochloridate followed by the addition of an excess of alcohol. 

This compound was designated E-600 by Schrader,3 who prepared it by the reaction of sodium p-nitrophenate on diethyl phosphorochloridate in xylene ... 

A thorough examination of the whole problem was carried out by Gardner and Heath. Using diethyl phosphorochloridate containing 32P, they prepared compound (VIII) thus ... 

Toy2 prepared this ester3 (as well as related esters) by the controlled hydrolysis of 2 mol. of diethyl phosphorochloridate ... 

When the monosodium salts of uracil and similar pyrimidines react with diphenyl phosphorochloridate, phosphorylation takes place on oxygen unless other suitable nucleophilic centres are present and free.69 The reaction between the sodium salt of a 1,3-dicarbonyl compound and diethyl phosphorochloridothionate yields the Z-vinylphosphorothionate if the tetrabutylammonium salt is employed, the product has E geometry. This phenomenon has been interpreted in terms of the shape of the... 

Diethyl chlorophosphate Phosphorochloridic acid, diethyl ester (8,9) (814-49-3) Isoamyl nitrite Nitrous acid, isopentyl ester (8) Nitrous acid, 3-methylbutyl ester (9) (110-46-3)... 

The etiolate intermediate, generated by the addition of higher-order cyanocuprates to enones, has been trapped with several electrophiles. Thus the addition of trimethylsilyl chloride, diethyl or diphenyl phosphorochloridate and iV-phenyltrifluoro methane-sulphonamide affords the corresponding vinyl silyl ethers, vinyl phosphates and vinyltri-flates. " ... 

Commercial diethyl phosphorochloridate [b.p. 60-62° (1.5 mm.)], purchased from Eastman Organic Chemicals, was distilled prior to use in this reaction. 

Phosphate groups can also be removed by dissolving-metal reduction. Reductive removal of vinyl phosphate groups is one of the better methods for conversion of a carbonyl compound to an alkene.150 151 The required vinyl phosphate esters are obtained by phosphorylation of the enolate with diethyl phosphorochloridate or NJ, N, N -tetra-methyldiamidophosphorochloridate.152 153... 

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