169 E-J.] 



BENZYL ISOTHIOCYANATE 



259 



[E.] Styrene [?J gives phenylchlor- 

 acetic acid and mandelic acid (see under 

 benzoic aldehyde [114; BJ). Sub- 

 sequent steps through benzylamine 

 with carbon disulphide as above under B. 



[F.] From phenol [6O] and carbon 

 disulphide [160]. Phenol and potassium 

 cyanide [172] give benzonitrile (see under 

 benzoic aldehyde [114 ; H]). 



[G.] From cymene [6] and carbon di- 

 sulphide. Cymene gives acetophenone 

 [114 ; K]. Then as above under A. 



[H.] From benzene [6; I, &c.] or 

 toluene [54] and carbon disulphide [160]. 

 All generators with these hydrocarbons 

 of acetophenone or benzonitrile referred 

 to under benzoic aldehyde [114 ; A] 

 become generators of benzylamine and, 

 with carbon disulphide, of benzyl 

 mustard oil. 



Aniline (from nitrobenzene) on dia- 

 zotisation with nitrous acid and inter- 

 action of the diazo-com pound with 

 nitromethane (see under hydrogen cyan- 

 ide [172 ; J, &c.]) gives, among other 

 products, phenylnitrom ethane = i 1 - 

 nitrotoluene (Bamberger, Schmidt, and 

 Levinstein, Ber. 33, 2053). The latter 

 reduces to benzylamine (Konowaloff, 

 Ber. 28, 1861). Toluene also on 

 nitration with nitric acid of i-ia sp. 

 gr. at 1 00 yields phenylnitrom ethane 

 (Ibid. loc. cit.j Journ. Buss. Soc. 31, 

 254). 



NOTE : For other methods of formation of 

 phenylnitromethane see Gabriel, Ber. 18, 1254 ; 

 Cohn, Ber. 24, 3867. 



Benzylamine is obtained from benzyl 

 chloride and alcoholic ammonia (Canniz- 

 zaro, Ann. 134, 128; Suppl. 4, 24; 

 Mason, Trans. Ch. Soc. 63, 1313; 

 Limpricht, Ann. 144, 305 : see also 

 Seelig, Ber. 23, 2971 ; Dhommee, Comp. 

 Rend. 133, 636); also from benzyl chlor- 

 ide and potassium cyanide [172] through 

 benzyl cyanide and hydrolysis of the 

 latter to phenylacetamide (Purgotti, 

 Gazz. 20, 173; 593), which gives 

 benzylamine by action of bromine in 

 presence of potassium hydroxide (Hof- 

 mann, Ber. 18, 2738 ; Hoogewerff and 

 Van Dorp, Rec. Trav. Ch. 5, 253). 



Or benzyl chloride or iodide interacts 

 with silver nitrite to form phenylnitro- 



methane (Holleman, Rec. Tr. Ch. 13, 

 405 ; Hantzsch and Schultze, Ber. 29, 

 700 ; Van Raalte, Rec. Tr. Ch. 18, 383), 

 which can be reduced to benzylamine as 

 above. 



Or benzyl chloride or bromide and 

 silver cyanate give benzyl isocyanate 

 (Letts, Journ. Ch. Soc. 25, 446 ; Ber. 

 5, 91 ; Strakosch, Ber. 5, 692 ; Laden- 

 burg and Struve, Ibid. 10, 46). Silver 

 cyanate is obtained from potassium 

 cyanate by double decomposition 

 (Mendius, Jahresber. 1860, 17); the 

 potassium salt is obtained by the oxida- 

 tion of potassium cyanide or ferrocyanide 

 [172] (Wohler, Berz. Jahresber. 3, 78; 

 4, 92; Pogg. Ann. 1, 117; Liebig, 

 Ann. 38, 108 ; 41, 289; Kolbe, Ann. 

 64, 237; Clemm, Ann. 66, 382; Wurtz, 

 Ann. Chim. [3] 42, 44 ; Lea, Jahresber. 

 1861, 789; Bell, Ch. News, 32, 100; 

 Gattermann, Ber. 23, 1224; Volhard, 

 Ann. 259, 378 ; H. Erdmann, Ber. 26, 

 2438 ; Reychler, Bull. Soc. [3] 9, 

 427). 



Benzyl isocyanate gives benzylamine 

 on decomposition by caustic alkali 

 (Cannizzaro, Ann. 134, 128 ; Strakosch, 

 Ber. 5, 692 : see also Letts, Ibid. 91). 



Benzylamine can be obtained also 

 from benzyl chloride and acetic acid 

 through benzylacetamide (Rudolph, Ber. 

 12, 1297), and decomposition of the 

 latter with alcoholic potash (Ibid.]. 



Or from benzyl chloride and formic 

 aldehyde [9l] through the aldehyde or 

 through ' trioxymethylene ' and the 

 base, hexamethylenamine, formed by the 

 action of ammonia on the aldehyde or 

 on trioxymethylene (Butleroff, Ann. 

 115, 322 ; Wohl, Ber. 19, 1842 ; Grassi- 

 Cristaldi and Motta, Gazz. 29, 43). The 

 compound of hexamethylenamine and 

 benzyl chloride gives benzylamine on de- 

 composition with alcoholic hydrochloric 

 acid (Delepine, Comp. Rend. 124, 292 ; 

 Bull. Soc. [3] 17, 294). 



[I.] Naphthalene [12] is a generator 

 of benzonitrile through phthalic acid 

 and phthalimide (see under benzoic 

 aldehyde [114 ; J]). 



[J.] From cumic aldehyde [116 ] 

 through isopropylbenzene and aceto- 

 phenone, &c. [114; K]. 



S 2 



