Rigg. — Montan Wax. 271 



Ryan and Dillon* gave the formula for montanic acid as C 28 H 56 Cv 

 The non-saponifiable portion they found to melt at 58-59°, and the analysis 

 gave 2-5 per cent, of oxygen, which agrees approximately with the formula 

 C 42 H M6 of Eisenreich. They also stated that no primary or secondary 

 alcoholic group is present in the substance. 



The work of previous observers may therefore be summed up as 

 follows : (a.) Three investigators have assigned to montanic acid the 

 formula C 29 H 58 2 , while one investigator has assigned the formula 

 C 28 H 50 O 2 to the same acid; (b.) von Boyen first stated that the non- 

 acid constituent was an unsaturated hydrocarbon, afterwards that it was. 

 an alcohol. Eisenreich and also Ryan and Dillon state that the non-acid 

 constituent is not alcoholic in nature, but regard it as an oxygenated 

 compound. 



In the present paper it is shown that : (1) the " montanic acid " occurring 

 in the wax is in reality a mixture of three acids — cerotic (C 26 H 62 2 ), mon- 

 tanic (C 28 H 56 2 ), and melissic (C 30 H 60 O 2 ) acids; (2) the non-saponifiable 

 portion is an olefinic hydrocarbon, probably C, 8 H 56 or C 26 H 52 , both of 

 which, being olefines, would have, of course, the same percentage com- 

 position. 



Cerotic and melissic acids were described by Brodie| as constituents 

 of beeswax, but have not hitherto been found in any mineral substance. 

 The separation of these acids was tedious, involving a series of over forty 

 fractional precipitations by magnesium acetate, whereby the cerotic and 

 melissic acids were obtained in a state of purity. 



Montanic acid, the acid of intermediate molecular weight, was isolated 

 by conversion of the crude acid into its ethyl salt, and subsequent distillation 

 under reduced pressure. Some fifteen fractionations were needed before 

 the substance could be considered pure. 



After purification, the cerotic and montanic acids both crystallized in 

 pearly scales. Hitherto cerotic and montanic acids have been described 

 as crystallizing in needles ; and the crude acids certainly do so, but the pure 

 acids crystallize in scales, and in so doing resemble all the lower members 

 of the higher fatty acids which have been obtained in a state of purity. 



There can be little doubt that cerotic, montanic, and melissic acids belong 

 to the homologous series of the higher fatty acids, and that these acids are 

 all normal fatty acids. A comparison of the physical properties of a number 

 of their derivatives supports this (Tables I— III, p. 285). In the case of 

 montanic acid it has been possible to show that the substance is undoubtedly 

 normal heptacosane carboxylic acid. 



The occurrence of montan wax as the principal product of steam distil- 

 lation of bituminous coal is of great interest. Kramer and SpilkerJ have 

 shown that fats and waxes, if distilled under pressure, yield mixtures of 

 hydrocarbons not unlike many natural petroleums, and they have suggested 

 that some petroleums at least owe their origin to the decomposition of wax 

 derived from algae. 



At first it appears difficult to imagine such supplies of wax in nature 

 as, by decomposition, would give rise to the immense quantities of oil present 

 m the large oilfields. Brown coal is, however, even more widely distributed 



* Sci. Proc. Roy. Dub. Soc, vol. 12, p. 20, 1909. 



t Phil. Trans. Roy. Soc, 1848. 



% Berichte, vol. 32, 1899, and vol. 35, 1902. 



