- 164 — J 



ment of the diamide with sodium nitrite in a solution of fuming nitric 

 acid gave rise to cis-trans-camphoric acid (m. p. 170 to 171°). Reaction 

 of chloro-camphoric acid chloride with ammonia led to chlorocamphor- 

 sec.-tert.-nitrilic acid (m. p. above 250°, but not very sharp). Bredt has 

 also discovered that from a solution of chlorocamphor nitrilic acid in 

 sodium carbonate, camphano nitrile (m. p. 139,5 to 141°) separates out 

 after prolonged standing. With alkali solution, the camphanonitrile first 

 splits up into a salt of hydroxycamphor nitrilic acid. After prolonged 

 action this is partly converted into camphononic acid and partly saponified 

 into hydroxycamphor aminic acid, which, when acidulated, forms camphanic 

 acid amide. In conclusion, Bredt reports on camphodinitrile (camphoric 

 acid nitrile), a body which was as yet unknown, although camphoric acid 

 ranks as one of the most thoroughly and frequently investigated dibasic 

 acids. Bredt allowed phosphorus pentachloride to act upon camphor-sec- 

 tert-nitrilic acid in a solution of low boiling ligroin. The residual mass 

 remaining after distilling off the ligroin and the phosphorus oxychloride 

 he treated with ammonia, which gave rise to camphor-sec.-tert.-nltriWc 

 acid amide. When heated with phosphorus pentachloride this nitrilic acid 

 amide yields camphodinitrile, m. p. 160°. 



Nitrogenous bodies. 



Mustard oil. In continuing his synthetical research in the fatty- 

 aromatic series 1 ), J. v. Braun 2 ) has incidentally prepared a number of mustard 

 oils. In this work he started with the thiurame disulphides (II) which are 

 formed from the salts of the dithiocarbamates (I) (from the amines and 

 carbon disulphide) by oxidation with iodine, and which, when treated 

 with alcoholic sodium ethylate, yield sodium compounds (III). Under the 

 continued influence of iodine these are converted into mustard oils (V) 

 with formation on a liberal scale of unstable cyclic sulphides (IV) as 

 intermediary products. All these reactions are carried out without diffi- 

 culty in the cold. 



NHR-C<f 



X SH, 



/SH, 



NHR-C< 









NH 2 

 NH 2 



(I) 



•R ^ SC(:S)NHR 

 •R + ' 2 ** SC(:S)NHR 



SC(:NR)SNa 

 > SC(:NR)SNa 

 (ill) 





h 



SC(:NR)S S:C: 

 SC(:NR)S ""* S:C: 



N-R + S 

 N-R + S 







(IV) 



(V) 



1 ) Comp. Report April 1912, 181, 182. 



2 ) Berl. Berichte 35 (1912), 2188. 



