150 



Report of Schimmel Q Co. April 1913. 



as a result of his own researches, that bergaptene is a coumarin-coumarone derivative, 

 and had suggested that one of the formulae I, II and III, set forth below might apply 

 to it. A. Tschirch 1 ) assigns to bergaptene formula II, but without adducing evidence 

 for his belief. Thorns has now acquired the conviction that the structure shown in 

 formula I is the correct one for bergaptene. In collaboration with Baetcke he has 

 reduced nitrobergaptene to amino-bergaptene (m. p. 198°) by warming it with tin and 

 hydrochloric acid, and from the reduced substance, by oxidation with sodium bichromate 

 and sulphuric acid in the cold, he obtained a body CnH0 5 , crystallising in gold- 

 coloured crystals, m. p. 248 to 250°. It contained neither methoxyl nor nitrogen, 

 hence it is clear that in the process of oxidation the amino-and the methoxyl-groups 

 were split off from the amino-bergaptene, and were each replaced by one oxygen atom. 

 Seeing that as a rule the elimination of such groups and their replacement by oxygen 

 takes place in the para-position, it may be concluded that, since bergaptene is a 

 phloroglucin-derivative, its substitution-products are arranged as shown in formula I. 

 By a similar method the nitroxanthotoxin was converted from primarily-produced 

 aminoxanthotoxin (m. p. 236°) into the same quinone, m. p. 248 to 250°; hence xantho- 

 toxin possesses the constitution expressed in formula V. When quinone is boiled with 

 sulphurous acid it yields the corresponding hydroquinone, of which the diphenylurethane 

 melts between 229 and 230° and the diacetyl derivative between 208 and 209°. 



OCH 3 



CH-O-L 



CH:CH 



I 



o-co 



Bergaptene. 



CH 



CH-0 



O 



OCH, 



O- 



CH : CH 



ii. 



OCH; 



•CH:CH 



I 

 •O — CO 



o 



•CH:CH 



( ycH 



1 



S 



•O-CO 



COO-L J-O-CH 





\ 1 





CH:CH 



IV. Quinone from bergaptene and xanthotoxin. 



OCH, 



/O 

 CH:CH 



•O-CO 



\ 

 •CH:CH 



V. Xanthotoxin. 



Oxides. 



A few years ago we referred to a paper by N. Prilechajeff 2 ) on the preparation 

 of the oxides and peroxides of various terpene bodies. Afterwards we were able to 

 establish the presence of one of these oxides, viz., linalool oxide 3 ), in linaloe oil. 

 Prilechajeff 4 ) has now published full particulars of the properties of these interesting 

 bodies, and the following particulars are taken from his paper: — 



Geraniol monoxide absorbs water in the presence of traces of an acid, giving rise 

 to a glycerol C 10 H 17 (OH) 3 : b. p. 204 to 206° (19 mm.), d^ 1,0486, n D160 1,4935; triacetate, 



l ) Handbuch der Pharmacognosy, Leipzig 1912, Vol.11, p. 872. — 2 ) Berl. Berichte 42 (1909), 4811; Report 

 April 1910, 153. — 3 ) Report October 1912, 78. Our statement that we had isolated linalool oxide both from 

 Mexican and from Cayenne linaloe oil is founded upon an error. As a matter of fact we have detected it 

 in Mexican linaloe oil only. — 4 ) Journ. russ. phys. chem. Ges. 44 (1912), 613; Chem. Zentralbl. 1912, II. 2090. 



