Phosphorus III Cyanide

III) cyanide in 1863.2 A second article3 by these authors discussed in some detail the chemical reactions of this substance. No further comment has appeared in the literature on the preparation or the properties of this compound until recently.4 Synthesis was accomplished by mixing phosphorus (III) chloride and silver cyanide (in chloroform) and heating in a sealed tube for several hours at 120 to 140°. After cooling, the tube was opened and the chloroform and unreacted phosphorus (III) chloride removed by evaporation. The phosphorus (III) cyanide was then obtained from the residue by sublimation. The yield was reported to be about 85% by this method. 

Roesky et al. discovered unusual products arising from reactions of some phosphorus(III) cyanides, or P(III) halides and mercuric cyanide, with hexafluoroacetone <86CB2687>. Two of these have fused 1,5,2-dioxaphosphinine structures, (269) and (375). 

Metal cyanides react with organic halides (most commonly with iodine or bromine compounds), olefins, dimethyl sulfate, alkylsulfates (ROSO3M), diazonium salts, oxonium salts, and compounds of phosphorus(III) or arsenic(III) such as ER2CI (E = P or As, R = Et, OEt, Ph) to give isocyanide complexes ... 

In the presence of Triethylamine, PI3 or P2l4 effects the conversion of aldehyde oximes or primary nitro compounds to nitriles. For example, treatment of the aldoxime derived from phenylac-etaldehyde with 1 equiv of PI3 (CH2Cl2-Et3N, 25 °C, 15 min) affords benzyl cyanide in 83% yield (eq 10). Similarly, treatment of 1-nitrodecane with 2 equiv of PI3 (CH2Cl2-Et3N, 25 °C, 15 min) affords 1-cyanononane (82%) (eq 11). Other reagents for the direct conversion of primary nitro compounds to nitriles include Sn(SPh)4/Ph3P/DEAD, TMSI, Sulfur Dioxide and Phosphorus(III) Chloride. ... 

Tropic Acid. The constitution of both tropic and atropic acids is known from syntheses by Ladenburg et al. from acetophenone. The ketone (I) by treatment with phosphorus pentachloride was converted into a-dichloroethylbenzene (II), and this, by the action of potassium cyanide in alcohol, into ethoxycyanoethylbenzene (III), which on hydrolysis yielded ethylatrolactic acid (TV). The latter was converted by strong... 

Heating with the following solids, their fusions, or vapours (a) oxides, peroxides, hydroxides, nitrates, nitrites, sulphides, cyanides, hexacyano-ferrate(III), and hexacyanoferrate(II) of the alkali and alkaline-earth metals (except oxides and hydroxides of calcium and strontium) (b) molten lead, silver, copper, zinc, bismuth, tin, or gold, or mixtures which form these metals upon reduction (c) phosphorus, arsenic, antimony, or silicon, or mixtures which form these elements upon reduction, particularly phosphates, arsenates,... 

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