Diethyl phosphorochloridate preparation

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

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 ... 

In preparation for the eventual removal of the undesired oxygen function at C-10 of 313 via a Birch reduction, the phenol 313 was phosphorylated with diethyl phosphorochloridate in the presence of triethylamine to give 314, which underwent stereoselective reduction with sodium borohydride with concomitant N-deacylation to deliver the amino alcohol 315. N-Methylation of 315 by the Eschweiler-Clarke protocol using formaldehyde and formic acid followed by ammonolysis of the ester group and acetylation of the C-2 hydroxyl function afforded 316. Dehydration of the amide moiety in 316 with phosphorus oxychloride and subsequent reaction of the resulting amino nitrile 317 with LiAlH4 furnished 318, which underwent reduction with sodium in liquid ammonia to provide unnatural (+)-galanthamine. 

Preparation.1 Potassium (-butoxide in THF is treated with dry ice to form potassium r-butylcarbonate (1) diethyl phosphorochloridate (2, Stauffer Chemical Co.)... 

The first example of this most important group of phosphorus esters, diethyl-p-nitrophenyl phosphate (paraoxon, 15), was prepared by Schrader (1948a) by the reaction of diethyl phosphorochloridate (16) with sodium p-nitrophenolate ... 

Demeton-S (56) can also be prepared directly by the reaction of sodium 0,0-diethyl phosphorothioate with ethyl-2-chioroethyl sulfide or by the reaction of diethyl phosphorochloridate with sodium 2-ethylthioethyl mercaptide (Schrader, 1950a 1950b). 

According to the original process of Addor (1962), phospholan is prepared by the reaction of ethylene-1,2-dithiol with cyanogen chloride, followed by the reaction of 2-imino-l,3-dithiolane (103) with diethyl phosphorochloridate. According to his later process (1970), N-(0,0-diethylphosphoryl) dithiocarbamate (104), obtained by the addition reaction of diethyl phosphoryl isothiocyanate and potassium hydrosulilde, is cyclised with ethylene bromide. 

A new peroxyphosphate, (EtO)2P(0)OOCH(Me)Et, has been prepared from diethyl phosphorochloridate and sodium s-butylperoxide. ... 

In the synthesis of antibiotic alafosfaUn 82 (Scheme 47.36), organolithium reagent 149 was prepared by trans-metallation of an organotin precursor 148, which could be obtained in an enantiopure form." Reaction of 149 with diethyl phosphorochloridate furnished intermediate... 

Interconversion of Carboxylic Acid Derivatives. Diethyl phosphorochloridate is useful for activation of carboxylic acids toward nucleophilic attack. Subsequent treatment of the phosphate ester with thallium sulfides produced thiol esters." Variations"" on this theme included prior formation of a heterocyclic phospho-nate followed by treatment with alcohols, amines, or thiols, thus providing a racemization-free method to prepare esters, amides, and thiol esters, respectively (eq 9),""" ... 

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

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 ... 

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