BASES DERIVED FROM THE PROTEINS 231 



out and patented but they are inferior to that outlined above 

 and have no practical value. 



p-Hydroxyphenylethylamine. — Since this substance is one of 

 the active principles in ergot, it is prepared synthetically (as 

 " tyramine "). Several methods of producing this and allied sub- 

 stances have been recorded in English and German patents. The 

 oldest synthesis (other than that effected by heating tyrosine) is 

 due to Barger {Journ. Chem. Soc. 1909, 95, 1 123) and involves the 

 reduction of /-hydroxyphenylacetonitrile, a substance obtained 

 from phenylacetonitrile (benzylcyanide) by successively nitrating, 

 reducing and diazotising : 



C 6 H 3 .CH 2 .CN -> N0 2 .C 6 H 4 .CH 2 .CN -> NH 2 . C 6 H 4 . CH 2 . CN -» 

 HO.C 6 H 4 .CH a .CN -> HO.C 6 H 4 .CH,.CH 2 .NH 2 



Another method, due to Rosenmund (Ber. 1909, 42, 4778), consists 



in condensing anisic aldehyde with nitromethane and reducing the 



compound that is formed ; the methyl group is then eliminated 



by boiling the methoxy-compound with iodhydric acid : 



CH 3 O.C 6 H 4 .CHO -> CH 3 O.C 6 H 4 .CH :CH.N0 2 -> 

 CH 3 O.C 6 H 4 .CH 2 .CH 2 .NH, -> HO . C S H 4 . CH 2 . CH 2 . NH 2 



Hordenine. — This alkaloid, which occurs in barley germs, 



has also to some extent been applied therapeutically. It has 



been synthesised by Barger {Journ. Chem. Soc. 1909, 95, 2193) 



by acting on phenylethylalcohol (a commercial product) with 



phosphorus pentachloride and heating the chloride that is found 



with dimethylamine ; the base thus produced is converted into 



hordenine by nitrating it, then reducing, diazotising, etc. : 



C 6 H s .CH 2 .CH 2 OH -> C 6 H 5 .CH 2 .CH 2 .C1 -> C 6 H 5 . CH 2 . CH 2 . N(CH 3 ) 2 -> 

 NO,.C a H 4 .CH 2 .CH 2 .N(CH 3 ) 2 -> NH 2 . C 6 H 4 . CH 2 . CH 2 N(CH 3 ) 2 -» 



HO . C 6 H 4 . CH 8 . CH , . N(CH 3 ) 2 



Rosenmund (Ber. 1910, 43, 306) has arrived at the same 

 result by methylating />-methoxyphenylethylamine prepared as 

 described above and then removing the methyl group : 



CH,O.C,H 4 .CH 2 .CH 2 .NH 2 -> CH 3 . C 6 H 4 . CH 2 . CH 2 . N(CH 3 ) 2 -» 



HO . C 6 H 4 . CH 2 . CH 2 . N(CH 3 ) 2 



The methylation is somewhat difficult to effect, on account ol 

 the variety of products it affords ; the direct methylation of 

 ^>-hydroxyphenylethylamine to hordenine by means of methyl- 

 iodide appears to be impossible, as hordenine methiodide is 

 formed ; it is said, however, that hordenine may be obtained by 

 the use of methyl chloride as methylating agent. 



Other Substances. — In addition to the three above-mentioned 



