458 On the Action of Sodium on Valerianic Ether. 



higher boiling-point, and by not being attackable by alcoholic 

 solution of potash, which very readily attacks valerianate of amyl. 

 (I have titrated valerianate of amyl on other occasions, and found 

 no difficulty in effecting the decomposition by means of alcoholic 

 potash.) 



The result, therefore, of the fractionation of the oily product 

 was, that it consisted of about equal parts of unaltered valerianic 

 ether and new product. Taking advantage of the unalterability 

 of the new product by alcoholic potash and the easy decompo- 

 sition of valerianic ether by this reagent, I made a titration of 

 the original oily product in order to ascertain the relative pro- 

 portions of valerianic ether and new product. 100 parts of the 

 oil saturated 14-8 parts of potassium. The theory for pure va- 

 lerianate of ethyl being 30'08, it follows that about half of the 

 oil consisted of that ether — a result which confirms the conclu- 

 sion drawn from the fractionation. 



Collecting the experimental results we have :— 



Valerianic ether employed = 30'4 

 Sodium used up ... = 5 '8 

 Sodium found caustic . = 5'13 



The quantities required by theory in order to give one mole- 

 cule of valerianic ether and one equivalent of sodium are — 



grins. 

 Valerianic ether .... 30*4 

 Sodium used up . . . . 5*38 

 Sodium caustic .... 5*38 



The experiment therefore accords sufficiently with this theory. 

 As many molecules of valerianic ether are employed as equiva- 

 lents of sodium, and all the sodium is ultimately caustic. 



19 grms. of oil, which on prolonged exposure in vacuo became 

 18*1 grms., were yielded by these materials. This oil consisted 

 of 9 grms. of polyvaleral (?iC 5 H 10 0), the rest being unchanged 

 valerianic ether. Of course there must have been much loss of 

 valerianic ether by the evaporation off of the 70 cubic centims. 

 of common ether ; so the unaltered valerianic ether experi- 

 mentally found must have been considerably less than that actu- 

 ally present. 



Furthermore, about half of the ethyl which was taken in the 

 form of valerianic ether was afterwards found in the form of 

 alcohol associated with the caustic soda. 



These experimental data prove the following equation to be a 

 correct expression of the reaction between sodium and valerianic 

 ether at a gentle heat, and in presence of much common ether. 



