20 THE SIMPLER NATURAL BASES 



[1909, I] also isolated the base after putrefying the mixture of ammo- 

 acids obtained by boiling caseinogen with sulphuric acid. 



Henze [1913] has made the most interesting observation that 

 p-hydroxyphenyl-ethylamine occurs in the salivary gland of Cephalo- 

 poda and has a paralysing action on crabs, which are the chief food of 

 these Molluscs. 



Syntheses. 



Larger quantities of p-hydroxy-phenyl-ethylamine are obtained 

 by synthesis, most conveniently by the reduction of p-hydroxy-phenyl- 

 acetonitrile with sodium and alcohol (Barger [1909, i]), according to 

 the equation : 



OH . C 6 H 4 . CH 2 . CN + 4 H = OH . C 6 H 4 . CH 2 . CH 2 . NH 2 . 



Two other syntheses of this amine were described by Barger and 

 Walpole [1909, 2]; according to one of these benzoyl-phenyl-ethyl- 

 amine is nitrated and the p-nitro-derivative is reduced, diazotised, and 

 hydrolysed : 



C 6 H 5 . CH 2 . CH 2 . NH . CO . C 6 H 5 ->NO 2 . C 6 H 4 . CH 2 . CH 2 . NH . CO . C 6 H 5 

 -NH 2 . C 6 H 4 . CH 2 . CH 2 . NH . CO . C 6 H 5 -OH . C 6 H 4 . CH 2 . CH 2 . NH . CO . C 6 H 6 

 -OH - . C 6 H 4 . CH 2 . CH 2 . NH 2 . 



The other synthesis starts from anisaldehyde which is successively 

 converted into p-methoxy-phenyl-acrylic acid, p-methoxy-phenyl- 

 propionic acid, and its amide, p-methoxy-phenyl-ethylamine and p- 

 hydroxy-phenyl-ethylamine : 



CH 3 O . C 6 H 4 . CHO->CH S O . C 6 H 4 . CH : CH . COOH->CH 3 O . C 6 H 4 . CH 3 . CH 2 . COOH 

 _CH 3 O . C 6 H 4 . CH 2 . CH 2 . CO . NH 2 -CH 3 O . C 6 H 4 . CH 2 . CH 2 . NH 2 

 -5.0H . C 6 H 4 . CH 2 . CH 2 . NH 3 . 



The yield by the last synthesis is poor ; the p-methoxy-phenyl- 

 ethylamine is better prepared by Rosenmund's method [1909], by 

 the reduction of the condensation product of anisaldehyde with nitro- 

 methane : 



CH 3 . C 8 H 4 . CHO + CH 3 . NO 2 = CH 3 O . C 6 H 4 . CH : CH . NO 2 

 -CH 8 . C 6 H 4 . CH 2 . CH : NOH-CH 3 O . C 6 H 4 . CH 2 . CH 2 . NH 2 . 



Rosenmund then boils the latter compound with colourless hydriodic 

 acid and obtains p-hydroxy-phenyl-ethylamirie. 



Hordenine, OH . C 6 H, . CH 2 . CH 2 . N(CH 3 ) 2 . 

 An infusion of barley germs, a by-product obtained in the pre- 

 paration of malt, had been employed in the South of France against 

 dysentery. This led to the isolation by Leger [1906, l] of an 

 "alkaloid" from barley germs, which he named hordenine. The 

 base was found by Leger [1906, 2,3, I9O7] and independently also 

 by Gaebel [1906] to be p-hydroxy-phenyl-ethyl-dimethylamine 



~ 2 . CH a . N (CH 3 ) 2 



