258 



SULPHUR COMPOUNDS 



[169 A-D. 



give the mustard oil by the general 

 method (Hof matin, Ber. 1, 301). 



Benzamide,f rom ammonium benzoate 

 or from benzoyl chloride and ammonia, 

 gives benzylamine among the products 

 of its electrolytic reduction in sulphuric 

 acid (Baillie and Tafel, Ber. 32, 71). 



Ethyl benzoate yields benzonitrile by 

 interaction with sodamide (Titherley, 

 Trans. Ch. Soc. 81, 1527). 



Benzoic acid also gives benzonitrile 

 through benzoyl chloride, and the inter- 

 action of the latter with benzamide 

 (Sokoloff, Gerhardt's 'Traite, &c./ I, 

 383), or withpotassium thiocyanate [174] 

 or cyanate (Limpricht, Ann. 99, 117; 

 Schiff, Ann. 101, 93). Also by the 

 interaction of cyanogen bromide and 

 potassium benzoate (Cahours, Ann. 108, 

 319; Ann. Chim. [3] 52, 200), of ben- 

 zoic acid and potassium thiocyanate 

 (Letts, Ber. 5, 673) or lead thiocyanate 

 (Kriiss, Ber. 17, 1767). 



Also from benzoic and acetic acids 

 via acetophenone and mandelic acid (see 

 under benzaic aldehyde [114 ; G-]), and 

 then through phenylbrom- and phenyl- 

 amino-acetic acid and benzylamine, &c., 

 as below under B. 



Benzoyl chloride and metJrylaminerVol. 

 II] give methylbenzamide (Van Ham- 

 burgh, Rec. Tr. Ch. 4, 388), which, by 

 the action of phosphorus pentachloride, 

 yields an imidochloride (v. Pechmann, 

 Ber. 28, 2367). Benzenylmethylimido- 

 chloride on heating decomposes into 

 methyl chloride and benzonitrile (Ibid. 

 83, 611). The latter can be reduced to 

 benzylamine as above. 



[B.] From benzoic aldehyde [114] and 

 carbon disulpliide [160]. Benzaldoxime 

 by the action of acetic anhydride gives 

 benzonitrile (Lach, Ber. 17, 1571). Also 

 by the action of monopersulphuric acid 

 (Carols reagent: Bamberger andScheutz, 

 Ber. 34, 2023). Subsequent steps as 

 above. 



Or benzaldoxime gives benzylamine 

 directly on reduction with sodium 

 amalgam and acetic acid (Goldschmidt, 

 Ber. 19, 3232). 



Or the oxime (' syn-' or 'anti-') by the 

 action of chlorine in chloroform solution 

 gives benzhydroximic chloride (Werner 

 and Buss, Ber. 27, 2197), which, by 



interaction with hydroxylamine, yields 

 benzenyloxyamidoxtme, C G H 5 . C(:N . 

 OH) . NH . OH, and this gives benzo- 

 nitrile when treated with acetic anhy- 

 dride (Ley, Ber. 31, 2127). 



Or benzaldehyde cyanhydrin (from 

 the aldehyde and hydrogen cyanide [172]) 

 with alcoholic ammonia gives the nitrile 

 of phenylaminoacetic acid, from which 

 the acid can be obtained by hydrolysis 

 (Tiemann, Ber. 13, 383). The acid 

 yields benzylamine on dry distillation 

 (Tiemann and Friedlander, Ber. 14, 

 1969). Or the cyanhydrin hydrolyses 

 to mandelic acid (Winckler, Ann. 18, 

 310; Miiller, Ber. 4, 980; Wallach, 

 Ann. 193, 38), and this combines with 

 hydrogen bromide to form phenylbrom- 

 acetic acid (Glaser and Radziszewski, 

 Zeit. [2] 4, 142). The latter gives 

 phenylaminoacetic acid on heating with 

 aqueous ammonia (Stockenius, Ber. 11, 

 2002). 



Benzoic aldehyde with aqueous ammo- 

 nia yields ' hydrobenzamide ' (Laurent, 

 Ann. 21,130; Rochleder, Ann. 41, 89), 

 and the latter gives benzylamine (with 

 toluene) by reduction in alcoholic solu- 

 tion with sodium (O. Fischer, Ber. 19, 

 748). 



Benzoic aldehyde phenylhydrazone 

 reduces to benzylamine (and aniline) 

 with sodium amalgam and acetic acid 

 (Tafel, Ber. 19, 1928), or by electroly- 

 sis (Tafel and Pfeffermann, Ber. 35, 

 1510). 



Benzoic aldehyde and glycin [Vol. II] 

 give benzylamine when heated to 130 

 (Curtius and Lederer, Ber. 19, 2463; 

 Erlenmeyer, junr., Ber. 30, 1528). 



Benzylamine is among the products 

 formed by heating benzoic aldehyde with 

 ammonium formate [Vol. II] (Leuckart 

 and Bach, Ber. 19, 2128). 



[C.] Hippuric acid [Vol. II] gives 

 benzonitrile on heating per se or with 

 zinc chloride (Limpricht and Uslar, Ann. 

 88, 133; Gbssmann, Ann. 100, 74). 

 Subsequent steps through benzylamine 

 and with carbon disulphide as before. 



[D.] WIOOL pfonylacetic acid [Vol. II] 

 through the bromo-acid (Radziszewski, 

 Ber. 2, 208), the phenylamino-acid as 

 above under B, and benzylamine with 

 carbon disulphide as before. 



