— 122 — 



C 10 H 17 «SH is formed. This was also obtained by the direct action 

 of sulphur on camphyl magnesium chloride. Both products boiled at 

 normal pressure between 205 and 215 , and were identified as thio- 

 borneol, which at ordinary temperature possesses only a faint odour 

 at the same time like camphor and mercaptane, is almost insoluble in 

 water, but is absorbed by alkali liquor as well as by organic solvents. 

 When exposed to the air it oxidises to camphyldisulphide (C 10 H 17 ) 2 S 2 

 of the m. p. 121 which is insoluble in alkalies. By the action of mercuric 

 chloride on thioborneol in alcoholic solution, thiobornyl mercuric chloride 

 was obtained which decomposes above 300 without melting. 



Terpineol. O.Wallach 1 ) has continued his work on the terpineol 

 of the m. p. 32 02 ) designated by him as ^-terpineol, and has produced 

 by addition of NO CI, N 2 4 , and N 2 3 , the previously described 

 /?-terpineol nitrosochloride (m. p. 103 ), and also the nitrosate (m. p. 125 ), 

 and the nitrosite (m. p. about 7 8°), although the last-named only in 

 a small yield. For the further reactions the nitrosochloride was employed. 

 It appears that by the action of sodium methylate an hydroxy-oxime 

 is formed from it, for on boiling with acids, hydroxylamine and water 

 are split off, and a body of the composition C 10 H u O is formed. The 

 study of this body produced these difficulties, that according to the 

 conditions of the reaction, compounds were obtained which, although of 

 the same composition, yet a had different chemical behaviour. If the 

 assumed hydroxy-oxime is treated with weak acids (oxalic acid), an alde- 

 hyde is obtained, but when stronger acids are used (sulphuric acid) a ketone 

 results. The aldehyde C 10 H 14 O 2 is regenerated with oxalic acid from 

 its semicarbazone (m. p. 209 ), and boils at 96 (11 mm. pressure); 

 d 0,97; n Di9° 1,4952. The aldehydic character of the body C 10 H 14 O 

 was shown by the formation of an acid C 10 H 14 2 when it was heated 

 with silver solution. This is the first synthesis of an aldehyde of 

 the terpene-series through a nitrosyl chloride addition, product. The 

 ketone regenerated (with sulphuric acid 1 in 2) from the semicarbazone 

 had a menthone - like odour, and the boiling point 93 ° (13 mm. 

 pressure), 218 to 2.20 at atmospheric pressure; d 1,001; n D20° M937- 

 The compound is isomeric with carvone; the high specific gravity is 

 striking, for a ketone heavier than water has not yet been observed 

 in the terpene-series. The ketone is unsaturated. Wallach explains 

 the formation of the ketone by the occurrence of atomic or linking- 

 displacements , not by the fact that the aldehyde is perhaps formed 

 in the first instance, which would be the most obvious. With regard 





*) Liebig's Annalen 345 (1906), 127. 



2 ) Liebig's Annalen 324 (1902), 79; Report October 1902, 93; comp. also 

 Report April 1901, 74. 



