252 



SULPHUR COMPOUNDS 



[160 H-161 C. 



[H.] From trimethylamine [Vol. II] 

 through methyl chloride by heating 

 the hydrochloride to 326 (Vincent, 

 Journ. Pharm. [4] 30, 132; Jahresber. 

 1878, 1 135), and then as above under G. 



[I.] From formic acid [Vol. II] and 

 methyl alcohol [13] through methyl 

 formate (Volhard, Ann. 176, 133). 

 The latter on extreme chlorination gives 

 perchlormethyl formate (Hentschel, 

 Journ. pr.Ch. [2] 36, IOO; 214; 305), 

 and this decomposes in contact with 

 aluminium chloride with the formation 

 of carbon tetrachloride (Ibid. 308). 



[J.] Allyl isothiocyanate [166] gives 

 carbon disulphide among the products 

 obtained by heating with water at i oo- 

 105 (Gadamer, Arch. Pharm. 235, 53). 



[K.] From gallic acid [Vol. 11] 

 through trichlor-aa-glyceric acid by 

 the action of hydrochloric acid and 

 potassium chlorate (Schreder, Ann. 177, 

 282). The trichloro-acid gives chloro- 

 form by the action of alkali in the cold. 



[L.] From salicylic acid [Vol. II] 

 through trichlor-aa-glyceric acid as 

 above. 



[M.] From phenol [60] through 

 trichlor-aa-glyceric acid as above. 



[N.] Benzene [6; I, &c.] by the action 

 of potassium chlorate and sulphuric acid 

 gives trichlorphenomalic acid, CC1 3 . 

 CO . CH : CH . CO 2 H (Carius, Ann. 

 142, 129 ; Kekule and Strecker, Ann. 

 223, 170; Anschiitz, Ann. 254, 152), 

 and this yields chloroform (with male'ic 

 acid) on heating with barium hydroxide 

 solution. Subsequent steps as under B. 



161. Methyl Mercaptan ; 

 Methaiiethiol ; Methyl Sulphydrate. 



CH 3 .SH 



NATUEAL SOUECES. 



Among the products of anaerobic 

 putrefaction of albumin (Nencki and 

 Sieber, Monats. 10, 526). The Bacilli 

 known to produce this compound from 

 serum albumin are Bacillus magnus, B. 

 spinosus, B. liquefaciens, and the anthrax 

 Clostridium. 



Occurs among the products of putre- 



faction of fish (Morner, Zeit. physiol. 

 Ch. 22, 514) and of elastin by anaerobic 

 micro-organisms (Zoja, Ibid. 23, 236). 

 Also among the products of in- 

 testinal decomposition of albumin (Ham- 

 marsten, ( Lehrbuch/ 3rd ed. 277) and, 

 possibly, in urine after taking asparagus 

 (Ibid. 480; Nencki, Arch. exp. Path. 

 17). 



A bacterium found in the urine of 

 a patient suffering from pneumonia and 

 albuminaria caused production of methyl 

 mercaptan (Karplus, Virch. Arch. 131, 

 2io ; Journ. Ch. Soc. 64, II, 335). 



Bacillus esterijicans isolated from 

 putrefying litmus solution and Bac. 

 prfBpollens from the intestinal contents 

 decompose peptone infusions with the 

 production of mercaptan (? methyl) 

 among other products (Maassen, Ch. 

 Centr. 1899, 2, 1058). 



A mercaptan (? methyl) is among the 

 products of the anaerobic putrefaction 

 of milk by Bacillus putrificus and by 

 the Bacilli of malignant oedema and 

 of symptomatic anthrax (Bienstock, 

 Ch. Centr. 1901, 1, 1209). 



SYNTHETICAL PEOCESSES. 



[A.] From methyl alcohol [13]. Sodium 

 methyl sulphate is distilled with potas- 

 sium hydrosulphide (Gregory, Ann. 15, 

 239; Obermeyer, Ber.20, 2918; Klason, 

 Ibid. 3407). 



[B.] From thiocyanic acid [174] and 

 methyl alcohol [13]. Potassium thio- 

 cyanate on distillation with calcium 

 methyl sulphate gives methyl thio- 

 cyanate (Cahours, Ann. Chim. [3] 18, 

 261 ; Ann. 61, 95). The latter on 

 heating to 180 yields (with the iso- 

 thiocyanate) methyl thiocyanurate (Hof- 

 mann, Ber. 13, 1349), and this on heat- 

 ing with ammonia gives (with mel- 

 amine) methyl mercaptan (Hofmann, 

 Ber. 18, 2758; Obermeyer, Ber. 20, 

 2919). 



[C.] Methyl sulphide [163] gives 

 methyl thiocyanate on heating with 

 cyanogen bromide (Cahours, Jahresber. 

 1875, 257). The latter is obtained by 

 the action of bromine on hydrogen 

 cyanide [172] or its salts (Serullas, 

 Beiz. Jahresber. 8, 94; Ann. Chim. 



