161 C-164 A.] 



METHYL MERCAPTAN 



253 



[2] 34, loo ; 35,294; 315; Langlois, 

 Ann. Suppl. I, 384; Ann. Chim. [3] 

 61, 482 ; Scholl, Beilstein's ' Hand- 

 buch/ I, 1434). 



[D.] From benzene [6; I, &c.] and 

 carbon disulphide [16O] through ani- 

 line and phenyl mustard oil by the 

 usual methods (Hofmann, Jahresber. 

 1858, 349; Ber. 2, 453; 15, 986; 

 Weith and Merz, Zeit. [2] 5, 589 ; 

 Rathke, Ber. 3, 861 ; Rudneff, Journ. 

 Russ. Soc. 10, 184; Werner, Trans. 

 Ch. Soc. 59, 400). The mustard oil is 

 reduced by aluminium amalgam to 

 diphenylthiourea and (through thio- 

 formaldehyde) methyl mercaptan (Gut- 

 bier, Ber. 34, 2033). 



162. Normal Butyl Mercaptan ; 

 n-Bu tanet hiol . 



2 . CH 2 CH 2 . SH 



NATURAL SOURCE. 



Occurs in the secretion of the Philip- 

 pine badger, Myclaus M!r<?^(Beckmann, 

 Pharm. Centr. 1896 [n. f.], 17, 557). 



NOTE : The secretion contains also n-butyl 

 sulphide, probably a product of oxidation of 

 the mercaptan (Ibid. 558). 



SYNTHETICAL PROCESS. 



[A.] From n-butyl alcohol [17] and 

 potassium hydrosulphide as above under 

 methyl mercaptan [161; A](Saytzef and 

 Grabowsky, Ann. 171, 251; 175, 348). 

 Or by the interaction of the n-butyl 

 haloid and potassium hydrosulphide, or 

 by distillation of the alcohol with phos- 

 phorus pentasulphide (general method ; 

 see Kekule, Ann. 90, 311). 



163. Methyl Sulphide. 

 (CH 3 ) 2 S 



NATURAL SOURCE. 



In American oil of peppermint 

 (SchimmePs Ber. Oct. 1896; Kleber, 

 Pharm. Rev. 14, 269 ; Gerber, Mon. 

 Sci. [4] 11, 880). 



SYNTHETICAL PROCESSES. 



[A.] ^YQTnm ethane [l] through methyl 

 chloride by chlorination (Berthelot, Ann. 

 Chim. [3] 52, 97), and interaction of 

 the latter with potassium sulphide (Re- 

 gnault, Ann. Chim. [2] 71, 391 ; Ann. 

 34, 2<5). 



[B.] From methyl alcohol [13] through 

 methyl chloride (Dumas and Peligot, 

 Ann. Chim. 61, 193 ; Groves, Journ. 

 Ch. Soc. 27, 641), and then as above. 

 Or by heating sodium methyl sulphate 

 with potassium sulphide (Klason, Ber. 

 20, 3407). 



[C.] From trimethylamine [Vol. II] 

 through methyl chloride by heating 

 the hydrochloride of the base to 326 

 (Vincent, Journ. Pharm. [4] 30, 132 ; 

 Jahresber. 1878, 1135). 



164. Ethyl Sulphide. 



(C 2 H 5 ) 2 S 



NATURAL SOURCE. 



Occurs in urine of dogs (Abel, Zeit. 

 physiol. Ch. 20, 253). 



SYNTHETICAL PROCESS. 



[A.] From ethyl alcohol [14] through 

 ethyl chloride or ethyl potassium sul- 

 phate, and the interaction of these with 

 potassium sulphide (Regnault, Ann. 

 Chim. [2] 71, 387 ; Loir, Comp. Rend. 

 26, 195; Riche, Ann. China. [3] 43, 

 297 : see also Dobereiner, Ann. 4, 172, 

 and Finckh, Ber. 27, 1239). 



NOTES -.Vinyl sulphide, (CH a : CH) a S, the chief 

 constituent of the oil ofAllium ursinum (Semmler, 

 Ann. 241, 92), does not appear to have been 

 synthesised, but could no doubt be prepared 

 from vinyl bromide and potassium sulphide by 

 the general method. 



Allyl sulphide, (CH 2 :CH. OH 2 ) 2 S, which is 

 generally stated to be a constituent of oil of 

 garlic, &c. (Wertheim, Ann. 51, 289 ; 55, 297 ; 

 Pless, Ann. 58, 36), according to Semmler 

 (Arch. Pharm. 230, 434) does not exist in 

 this oil, and is therefore most probably absent 

 from the other plant oils in which it is supposed 

 to have been found. 



