366 Action of Pentachloride of Phosphorus on Aldehyde. 



This action of pentachloride of phosphorus has been tried on 

 the aldehydes of the fatty acid series. 



By acting on oeuanthylic aldehyde, C^'^H^^O^ Liaipricht* 

 obtained chloroenanthole. Equal equivalents of pentachloride 

 of phosphorus and oeuanthole were mixed together and the pro- 

 duct distilled, and the part boiling above 150° C. collected se- 

 parately. This product, washed with water, then shaken with 

 bisulphite of ammonia, dried and rectified, yielded pure chlor- 

 oenanthole, C'* H^'^CP. The action was in accordance with the 

 equation — 



CHHi4 02 + PCP=Ci*Hi4CF + P02CR 



CEnanthole. Chloroenanthole. 



It is a transparent, mobile liquid, lighter than water, and boiling 

 at 191° C. Heated with sodium-alcohol in closed tubes to 

 250° C. it is decomposed into hydrochloric acid, raonochlori- 

 nated chloroenanthole, C'^H'^Cl, which boils at 155° C, and a 

 hydrocarbon of which the formula is probably C'^ H''^. Treated 

 with sodium, and then frequently rectified over bright metallic 

 sodium, chloroenanthole yielded the hydrocarbon C^"* H'"*. It is 

 a liquid boding at 95°, and with a peculiar odour. 



Ebersbachf in a similar manner has obtained the corrcsjiond- 

 ing compound C^^H'^CP from valeraldehyde. It is a transpa- 

 rent, mobile liquid, with a feeble and not unpleasant odour: it 

 has the specific gravity 1"05, is insoluble in water, and boils at 

 130°. Boiled with alcoholic potash it loses chlorine and yields 

 the compound Ci°H9Ch 



Geuther J examined the action of pentachloride of phosphorus 

 on common aldehyde. Aldehyde was added to pentachloride of 

 phosphorus in a retort which was kept cool, until only a slight 

 excess of that substance remained; a slight evolution of HCl 

 took place, arising from the presence of a trace of water in the 

 aldehyde. On applying heat, the whole dissolved up to a homo- 

 geneous liquid, which on being rectified gradually blackened. 

 When the temperature had reached 100° C. the receiver was 

 changed ; the distillate which then passed over was oxychlo- 

 ride of phosphorus. On mixing the distillate below 100° with 

 water, an oily body separated, which, when washed, dehydrated 

 over chloride of calcium and rectified, had the boiling-point GO°C. 

 The liquid has a sweetish fetherial smell and taste, strongly re- 

 sembling chloroform: at 4° it has the specific gravity 1-9. It 



* Liebig's Annalen, July 1857. 



t Ibid. June 1858. J Ibid. March 1858. 



