98 Report of Schimmel $ Co. April 1913. 



more recent investigators, such as Minovici 1 ) and Colson 2 ), the action of the antidote 

 in question is due to the formation of a peculiar non-toxic compound, so-called turpen- 

 tine-phosphorous acid. For the reasons abovementioned E. Sieburg 3 ) has set himself 

 the task of clearing up these contradictory views by an experimental chemical and 

 toxicological investigation. With this object in view, Sieburg ascertained by analysis 

 the conditions which govern the formation of the compound in question and its empirical 

 formula, and, by experiments with living animals, tested its action and its behaviour 

 in the animal organism. In view of the general interest which attaches to the 

 whole problem we deem it desirable to refer in some detail to the results of this 

 investigation. 



According to Sieburg, so-called turpentine-phosphorous acid is prepared as follows; 

 In a round flask on a boiling water-bath, from 2 to 5 p. c. (under circumstances 

 also 10 p. c.) of yellow phosphorus is dissolved in freshly-distilled or oxidised French 

 turpentine oil, by passing-in air. The solution is left standing for some time in open 

 dishes. The oil turns turbid and soon afterwards the turpentine-phosphorous acid separa- 

 tes out in the shape of a film. When this is removed another film forms, until all the 

 phosphorus is used up. From the fact that no film is formed when the reaction takes 

 place in filled and closed vessels it is to be inferred that the formation is due to the 

 action of atmospheric oxygen. When the filmy product is pressed it constitutes a 

 sticky, wax-like body, which after treatment with light petroleum appears as a colourless, 

 dry, powdery mass, incapable of being purified by crystallisation. At 82° the mass 

 is melted and, when exposed to air, it resinifies somewhat rapidly. According to 

 Sieburg its odour is peculiar and does not clearly remind of phosphorus; it dissolves 

 readily in alcohol, chloroform, and acetone, sparingly in light petroleum, ether and 

 benzene. With litmus-paper the solutions give an acid reaction. When dissolved in 

 alkalies, the body is precipitated again when hydrochloric acid is added. It exhibits 

 marked reducing properties towards alkaline solution of silver or copper. The author 

 assigns to the body the empirical formula CioH 17 P0 3 or Ci Hi 8 PO 3 4 ). The analysis 

 of the sodium-, barium-, and lead-salt shows the compound to be of the nature of 

 an unibasic acid. It does not absorb bromine. Oxidation with nitric acid gives rise 

 to phosphoric acid. When warmed to 100° the substance decomposes, giving off 

 phosphoretted hydrogen (?). When heated above 180° a faintly-yellow liquid free 

 from phosphorus passes over which, when brominated in carbon disulphide solution, 

 yields crystals, m. p. 96. These, Sieburg regards as pinoldibromide Ci Hi 6 Br 2 O. By 

 means of alcoholic potash the solid body was converted into a liquid with a faint 

 camphoraceous odour, b. p. 187°, which may be pinol Ci Hi 6 O. In view of the results 

 stated above Sieburg (herein differing from Minovici, who has assigned to the compound 

 the formula C10H15H2PO3), believes that the body should be regarded, not as a derivative 

 of phosphorous acid, but as one of hypophosphorous acid, possessing the structure 



/OH 

 P O . Hence he gives it the name of "pinolhypophospnorous acid". 



CxoH 1(; 



Pending the publication of the results of further investigations into the constitution 

 of this body we feel unable to share the author's view. In the first place, the fact that 

 pinol occurs when the decomposition takes place above 180° by no means proves that 



x ) Pharm. Zentralh. 45 (1904), 532. — 2 ) Compt. rend. 146 (1908), 817; Report November 1908, 124. — 

 a ) Biochem. Zeitschr. 43 (1912), 280. From a reprint kindly sent to us. — 4 ) The empirical formula C 10 H 18 PO 3 

 is theoretically quite out of the question. In that case it would have to be CxoHuiPOa. 



