286 Transactions. 



Part III. — Constitution of the Higher Fatty Actds. 



It has been shown in Part I that three acids — cerotie. montanie, and 

 melissie — exist side by side in montan wax. It was also shown in Part II 

 that the properties of these three acids are closely related, and that their 

 corresponding compounds are similar. It would hardly seem likely that 

 three such compounds, possessing properties so closely related, should 

 exist side by side in montan wax unless there be some simple constitutional 

 relationship between them. 



Experiments have been made to show the relation of these acids to one 

 another and also to acids lower in the series. 



(A.) The Relationship to Acids Lower in the Series. 



Mai* showed that when the barium salts of palmitic or stearic acid 

 were distilled with sodium methylate, hydrocarbons resulted. From 

 barium palmitate he thus obtained n.-pentadecan and from stearic acid 

 n.-heptadecan. 



If barium montanate is heated with sodium ethylate, it should, if it 

 behaves like palmitate and stearate of barium, give a hydrocarbon, 

 n.-heptacosane. C 27 H 5G . 



If this hydrocarbon is a normal primary paraffin it will be identical 

 with the compound obtained by Krafft by the reduction of myristone, 

 and montanie acid will then also contain a normal primary chain of carbon 

 atoms. It will still remain uncertain whether the carboxyl group is at 

 the end of the chain, for though the ease of bromination suggests that the 

 bromine enters the chain in the a position, it does not show that the 

 carboxyl group is at the end of the chain (isobutyric acid brominates 

 more readily than normal butyric acid). 



Calcium montanate when distilled with sodium ethylate gave a hydro- 

 carbon, which after recrystallizing melted at 56-5-57-5°. A sample of 

 normal heptacosane prepared by the reduction of the myristone with 

 hydriodic acid melted at 59-60°. When equal quantities of the two hydro- 

 carbons were mixed the product melted at 58-59°— i.e., half-way between 

 the two. There can, under these circumstances, be little doubt that the 

 hydrocarbon from montanie acid was only slightly impure n.-heptacosane, 

 otherwise the mixture would have melted almost for a certainty at a lower 

 temperature than the melting-point of the lower melting-point hydro- 

 carbon. 



(B.) The Relationship existing between the Three Higher Fatty Acids. 



Attempts were made to degrade montanie acid to cerotie acid, but, 

 although much work was done in this direction, no definite conclusion 

 has been arrived at. It was hoped that degradation would be effected 

 by the following procedure, which is based on that employed by Le Seur 

 in the degradation of stearic acid* : (a) Formation of a brommontanic 

 acid ; (h) production of the unsaturated acid direct, or the formation of 

 the a hydroxy acid and the conversion of this compound into the un- 

 saturated acid ; (c) the oxidation of the unsaturated acid into the lower 

 homologue. 



o 



* Berichte, vol. 22. 1889, p. 2133. 



