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XV. " Researches on the Phosphorus-Bases." No. XIV. Action 

 of Triethylphosphine on the Substitution- com pounds of 

 Marsh-Gas. By A. W. HOFMANN, LL.D., F.R.S. Re- 

 ceived May 24, 1861. 



The formation of diatomic bases by the action of triethylphosphine 

 on dibromide of ethylene, very naturally suggested the idea of study- 

 ing the deportment of the phosphorus-base with the numerous 

 brominated derivatives of the ethylene-series discovered by Cahours, 

 and lately examined again by A. Lennox. All these compounds act 

 indeed with extraordinary energy upon triethylphosphine ; the pro- 

 ducts, however, of these reactions are far from exhibiting, with regard 

 to the compounds from which they originate, the simplicity and inti- 

 macy of relation which theoretical speculation, based on the obser- 

 vation of the action of dibromide of ethylene, might lead us to expect. 

 Most of the brominated substitution-products are apt to lose either 

 bromine or hydrobromic acid, the bromides respectively of triethyl- 

 phosphine and of triethylphosphonium being formed, together with 

 secondary phosphonium-compounds of subordinate theoretical interest 

 which I have not investigated in detail. 



It still remained to study the deportment of the phosphorus- 

 bases with chlorine- and bromine-compounds of simpler constitution. 

 Hoping to obtain more characteristic results in this direction, I was led 

 to submit the compounds which are formed by the action of triethyl- 

 phosphine on some of the substitution-products of marsh-gas to a 

 more minute examination. 



The action of chlorine upon marsh-gas has been the subject of an 

 important investigation by Regnault, who has shown that the gradual 

 substitution of chlorine for hydrogen gives rise to the following series. 



Marsh-gas C H 4 Tetrahydride of Carbon. 



Monochlorinated marsh-gas .... C H 3 Cl Chloride of Methyl. 



Dichlorinated marsh-gas C H 2 C1 2 Bichloride of Methylene. 



Trichlorinated marsh-gas C H C1 3 Trichloride of For my 1. 



Tetrachlorinated marsh-gas .... C Cl 4 Tetrachloride of Carbon, 



I was anxious to ascertain whether these four chlorinated deriva- 

 tives, when submitted to the action of triethylphosphine, would fix 

 respectively 1, 2, 3 and 4 molecules of the phosphorus-base, giving 



