274 



APPENDIX 



[177-178. 



from the Japanese Valenana officinalis 

 var. angustifolia (B. and W. loc. cit. 18), 

 and in French oil of valerian (Oliviero, 

 Comp. Rend. 117, 1096; Bull. Soc. [3] 

 11, 150; 13, 917). d-Camphene is con- 

 tained in oil of ginger (SchimmeFs 

 Ber. Oct. 1893; B. and W. loc. cit.), 

 in oil of sweet orange (neroli oil from 

 flowers) (Theulier, Bull. Soc. [3] 27, 

 278 : see also Hesse and Zeitschel, 

 Journ. pr. Ch. [2] 66,481), in oil of 

 spike from Lavandula spica (Bouchardat, 

 Comp. Rend. 117, io94),and in American 

 oil of turpentine (SchimmeFs Ber. Oct. 

 1897 : see also Armstrong and Tilden 

 as below). 



i-Camphene occurs in oil of rosemary 

 (Gildemeister and Stephan, Arch. 

 Pharm. 235, 586; Schimmel's Ber. 

 Oct. 1897). 



A camphene is contained in Russian 

 oil of turpentine, probably from Abies 

 (Pinus) siblrica (Golubeff, Journ. Russ. 

 Soc. 20, 585; Ch. Centr. 1888, 2, 

 162,2), in French turpentine oil, and 

 probably in other pinene-containing 

 oils from Coniferse (Armstrong and 

 Tilden, Ber. 12, 1753; Trans. Ch. Soc. 

 35, 742 ; Power and Kleber, Pharm. 

 Rund. 12, 1 6; Bouchardat and Lafont, 

 Comp. Rend. 113, 551; 125, in). 



SYNTHETICAL PROCESSES. 



[A.] From borneol [176] by heating 

 with hydrogen potassium sulphate to 

 200 (Wallach, Ann. 23O, 239), or with 

 dilute sulphuric acid to 6o-ioo(Kono- 

 waloff, Journ. Russ. Soc. 32, 76). Or 

 borneol can be converted into bornyl 

 chloride by heating with hydrochloric 

 acid (Berthelot, Ann. 112, 366), or with 

 phosphorus pentachloride (Wallach, loc. 

 cit. 23 1 ; Kachler, Ber. 11, 460 ; Ann. 

 197, 93). The chloride gives camphene 

 on heating with alcoholic potash (Riban, 

 Ann. Chim. [5] 6, 383), with water and 

 magnesium oxide (Kachler, Ann. 197, 

 96), or with aniline (Wallach, loc. cit. 

 233; Ber. 25, 916). Water alone 

 decomposes the chloride with the forma- 

 tion of campheue (Kachler and Spitzer, 

 Ann. 200, 342 ; Riban, loc. cit. 382). 



[B.] Camphor [175] on heating with 

 ammonium formate gives formylbornyl- 



amine (Leuckart and Bach, Ber. 20, 104 ; 

 Wallach and Griepenkerl, Ann. 269, 

 347), and this yields bornylamine on 

 hydrolysis with hydrochloric acid. The 

 amine or its forniyl derivative gives 

 camphene on heating to 200-210 with 

 acetic anhydride (W. and G. loc. cit. 

 349). Or camphor by the action of 

 phosphorus pentachloride at ordinary 

 temperatures gives camphor chloride, 

 C 10 H 16 C1 2 (Spitzer, Ann. 196, 262), 

 and this on treatment with sodium in 

 ethereal solution yields a camphene 

 (Kachler, Ann. 197, 127 ; K. and 

 Spitzer, Ann. 200, 341 ; Montgolfier, 

 Ann. Chim. [5] 14, 104). 



Camphor oy the action of sodium 

 gives (with d-borneol) isoborneol (Ber- 

 tram and Walbaum, Journ. pr. Ch. [2] 

 49, 15), and this yields camphene on 

 heating in benzene solution with zinc 

 chloride or on boiling with dilute sul- 

 phuric acid (Ibid. 8). Isoborneol also 

 gives camphene by heating to 220 

 with zinc dust (Semmler, Ber. 33, 

 735)- 



NOTE : Bornylamine is among the products 

 formed by the reduction of camphoroxime with 

 sodium in alcoholic solution (Leuckart and 

 Bach, Ber. 20, 104: for electrolytic reduction 

 of the oxime to bornylamine, see Bohringer 

 and Sohne, Germ. Pat. 141346 ; Journ. Ch. 

 Soc. 84, I, 551). 



Camphor may also be converted into 

 borneol [as under 176, A], and the 

 latter treated as above under A. 



178. Mentheiie ; 

 Tetrahydro-p-Cyxnene ; 



l-Meth.yl-4-niethoethyl- 

 3-cyclohexene. 



CH, 



CH 



H 



"I 

 H 2 C 



CH 2 



I 

 CH 



C 

 . CH . 



NATURAL SOURCE. 



According to Labbe menthene is 

 contained in oil of thyme (Bull. Soc. 



