12 THE CHEMICAL CONSTITUTION OF THE PROTEINS 



resulted when hippuryl-aspartic acid azide was combined with glycine 

 ester. 



In conjunction with Gumlich, Curtius has investigated the linking 

 of hippurazide with /3-amino-a-oxypropionic acid and with /3-amino- 

 butyric acid. With the former compound, the combination took place 

 with the hydroxyl group instead of with the amino group, hippuryl-a- 

 oxy-/3-aminopropionic acid, 



C 6 H 5 . CO . NH . CH 2 . CO O CH . (CH 2 . NH 2 ) . COOH, 



being formed. With the latter, by the usual series of reactions they 

 prepared hippuryl-/3-aminobutyric acid and hippuryl-/3-aminobutyryl- 

 /3-aminobutyric acid. 



Curtius and Miiller have also prepared hippuryl-fy-aminobutyric 

 acid and hippuryl-/3-phenyl-a-alanine, compounds of no great interest 

 since these amino acids do not occur in the protein molecule. They 

 show, however, that not only can a-amino acids be combined together 

 by the azide method, but also ft- and 7- substituted amino acids. 



In order to build up chains containing the carbamic acid radical, 

 NH . CO, just as Curtius and his co-workers have built up chains con- 

 taining glycyl, NH.CH 2 .CO, alanyl and asparagyl radicals, Curtius 

 and Lenhard, in 1904, proposed to make use of the azide of hippuryl- 

 carbamic acid, 



C 6 H 5 . CO . NH . CH 2 . CO NH . CO . N 3 . 



This compound, however, was unavailable, since sufficient quantities 

 of hippuryl urea, which Curtius had formerly prepared from hippuric 

 ester and urea, could not be obtained from hippurazide and urea. 

 They therefore attempted to make the azide of benzoylcarbamic acid 

 by the action of hydrazine on benzoylurea, but the only product which 

 they obtained was the hydrazide of benzoic acid. The benzoic acid 

 radical is therefore very easily eliminated from the urea molecule, the 

 molecule of benzoylcarbamic acid hydrazide, being hydrolysed according 

 to the equation 



C 6 H 5 . CO . NH . CO . NH . NH 2 + H 2 O = C 6 H 5 . CO . NH . NH 2 + NH 3 + CO 2 . 



This non-success led them to attempt to combine phenylcarbamic 

 acid azide C 6 H 5 .NH.CO N 3 , which Curtius and Hofmann and 

 Curtius and Burkhardt had described in 1896 and 1898, with urea, but 

 again the desired result was not achieved, nor could a combination 

 of this compound with biuret be effected. 



It followed therefore that acid radicals cannot be combined with 

 urea by the acid azide reaction. 



