Spermine, Choline, Ergothioneine 165 



of distilled water; to the extract thus obtained (concentrated by 

 evaporation, if necessary), a very small drop of an aqueous saturated 

 solution of picric acid is added, by means of a platinum loop; after 

 a minute or two a cover slip is applied, and the preparation examined 

 under the microscope; 'when fully developed, the crystals have the 

 form either of obtuse or sharp-ended needles, or of rhombic prisms 

 frequently crossed by a refrangent line at their equator. Sometimes 

 crosses are formed, and more rarely stars.' (For further particulars 

 concerning Barberio's test see Harrison, 1932.) Another deriva- 

 tive of spermine used in medico-legal laboratories is spermine 

 flavianate; this crystalline compound forms the basis of Puranen's 

 reaction (Puranen, 1936; Berg, 1948). 



Synthesis of spermine 



The final elucidation of the chemical structure of spermine was 

 achieved in 1926. The existence of two chains A^ — C — C — C — A'^ 

 and of one chain N—C — C — C — C — A^ in the spermine molecule 

 was inferred by Dudley, Rosenheim and Starling from the identi- 

 fication of pyrrolidine and tetramethyltrimethylene diamine as 

 degradation products of spermine hydrochloride and decamethyl 

 spermine, respectively. In Wrede's laboratory, the presence of two 

 3C chains and one AC chain was established the same year as a 

 result of studies on split products obtained from spermine by oxidation 

 with molecular oxygen in presence of copper. The final proof was 

 provided by the English investigators when they accomplished the 

 synthesis of spermine and showed it to be, a,(5-bis [y'-amino- 

 propylamino]-butane: 



CHaCH.CHa CH.CH2CH2 



I ■ I II 



NH2 NHCH2CH0 CH2CH2 NH NH2 



Spermine 

 The oxidation of spermine gives rise to a volatile base associated 

 with the characteristic odour of semen. The appearance of the 

 semen-like odour during treatment of spermine chloroaurate with 

 metallic magnesium, first described by Schreiner (1878), probably 

 involves also an oxidation. The base is volatile in steam, and forms 

 a crystalline hydrochloride and chloroaurate (m.p. 204-206°); it is 

 probably identical with A^-y-aminopropylpyrroline. 



