Diethyl cyanophosphonate

In a 50-mL, round-bottomed flask, equipped with a rubber septum and a magnetic stirring bar and filled with argon, are placed citronellic acid (112 mg, 0.658 mmol) and a solution of (R)-1-(1-naphthyl)ethylamine (140 mg, 0.818 mmol) (Note 29) in dry DMF (4 mL) (Note 5). To this mixture in an ice bath are added a solution of diethyl cyanophosphonate (224 mg, 1.37 mmol) (Note 30) in dry DMF (2 mL) and then dry triethylamine (0.1 mL). The mixture is stirred and the reaction is followed by TLC. When the carboxylic acid has been consumed, which takes approximately 2 hr at room temperature, the reaction mixture is dissolved in a mixture of benzene (5 mL) and ethyl acetate (5 mL). The mixture is washed successively with cold 5% hydrochloric acid,... 

Commercial grade diethyl cyanophosphonate is distilled under argon before... 

Diethyl cyanophosphonate Phosphonic acid, cyano-, diethyl ester (9) (2942-58-7)... 

The reaction of m-fused perhydropyrido[2,l-6][l,3]oxazines (31) with diethyl cyanophosphonate in the presence of a catalytic amount of ZnCl2 or ZnBr2 provided 2-cyanopiperidines (32) [88H(27)1575 91SL44, 91SL878]. 

Aldehydes, RCHO, have been cyanophosphorylated with diethyl cyanophosphonate [NC-P(=0)(0Et)2] to give cyanohydrin O-phosphonates, R- CH(CN)-0P(=0)-(OEt)2, in up to 98% yield and 97% ee, using a YLi3(BINAP)3 catalyst.255... 

Alkylation of the a-aminonitrile (49) with propyl bromide followed by reductive decyanation gives the key intermediate (50), which on treatment with diethyl cyanophosphonate leads to the formation of a new a-aminonitrile (51). Compound (51) reacts with K and 18-crown-6 in THF to form gephyrotoxin-223AB, an indolizidine alkaloid (Scheme 24). ... 

Mukaiyama, T., Masutani, K., Hagiwara, Y. Preparation of nitriles from primary alcohols by a new type of oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone and diethyl cyanophosphonate. Chem. Lett. 2004, 33, 1192-1193. 

PHoaPHONATE MODincATioN Diethyl cyanophosphonate. Tetraethyl phosphorosuccinate. Triethyl phosphine. Triethyl phosphite. Triethylphosphonoacetate. 

Optically pure cyanohydrins serve as highly versatile synthetic building blocks [24], Much effort has, therefore, been devoted to the development of efficient catalytic systems for the enantioselective cyanation of aldehydes and ketones using HCN or trimethylsilyl cyanide (TMSCN) as a cyanide source [24], More recently, cyanoformic esters (ROC(O)CN), acetyl cyanide (CH3C(0)CN), and diethyl cyanophosphonate have also been successfully employed as cyanide sources to afford the corresponding functionalized cyanohydrins. It should be noted here that, as mentioned in Chapter 1, the cinchona alkaloid catalyzed asymmetric hydrocyanation of aldehydes discovered... 

Guzman. A., and Diaz, E., A convenient method for the phosphorylation of phenols with diethyl cyanophosphonate, Synth. Commun., 27, 3035, 1997. 

Diethyl cyanophosphonate converts quinoline and isoqninoline iV-oxides into the 1- and 2-cyano-heterocycles in high yields in a process which must have 0-phosphorylation as a first step, and in which the elimination of diethylphosphate may proceed via a cyclic transition state trimethylsilyl cyanide and diazabicyclonndecene effect the same transformation. A chloroformate and an alcohol convert the iV-oxides into ethers, as illustrated below for isoquinoline iV-oxide, a chloroformate and a Grignard reagent prodnce 2-snbstitnted quinolines, and a chloroformate then an isonitrile produce 2-carbamoyl-... 

Diethyl phosphoryl cyanide or diethyl cyanophosphonate (3) activates carboxylic acid (1) and serves as a coupling agent with amine (2) to provide amide or peptide (4).1-3... 

Diethyl cyanophosphonate is also known as diethylphosphoryl cyanide, diethoxy-phosphoryl cyanide, diethylphosphorocyanidate, diethyl cyanophosphate, and DEPC.13 It can be readily prepared from triethyl phosphite and cyanogen bromide.2 It is very toxic and corrosive and it must be handled in a fame hood. The reagent is moisture sensitive and should be stored under nitrogen in a refrigerator. 

The addition of NEt3 to carboxylic acid 1 generates carboxylate anion which attacked at phosphorus of diethyl cyanophosphonate and subsequently displaces -CN to produce activated carboxylic acid phosphate ester 5. Nucleophilic addition of amine 2 to phosphate ester 5 gives the amide 4 and diethylphosphate.1-3... 

The GaN HEMT sensors were tested with DECNP (Diethyl cyanophosphonate, a Tabun simulant), sulfur hexafluoride (Sp6, a nerve agent stimulant), and common chemical solvents including diethyl ether, dichloromethane, ethyl acetate, acetonitrile, acetone, and benzene. To measure sensor responses, drain current (Ids) of a GaN HEMT was monitored at a constant drain voltage (Vds) and a constant gate voltage (Vgs) during exposures to various gaseous environments. 

Source-drain current (IjJ of the GaN HEMT sensor was measured during exposures to diethyl cyanophosphonate (DECNP), a Tabun simulant, at room temperature (a) 90 s exposures to 0.1% DECNP in N2, and (b) a 30 s exposure to 10 ppm DECNP. Measurements were made with of 1.5 V and... 

The use of diethyl phosphoryl cyanide (diethyl cyanophosphonate) for the activation of carboxylic acids. 

To avoid the intrinsic instability of cyanohydrins and their silyl ether, Saa and coworkers reported catalytic asymmetric cyanophosphonylation reaction of aldehydes with commercially available diethyl cyanophosphonate [58]. In these works, Lewis acid-Lewis base bifunctional catalyst (65) prepared by mixing BI-NOLAM ligand with amino arms as Lewis base and Et2AlCl was found to work nicely (Scheme 6.46). Since a strong positive nonlinear effect was observed in this reaction, actual catalyst is in equilibrium with some oligomeric species of the aluminum complexes. Bifunctional catalyst (65) could also catalyze cyanosilylation of... 

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