Polyamines, viii

The venoms of many kinds of bees, wasps, and hornets (the genera Vespa, Polistes, Vespula, Ropalidia, etc.) contain biogenic amines such as histamine (136), serotonin (141), and catecholamines in addition to polyamines such as putrescine (111), spermidine (110), and spermine (112) (Table VIII). The biogenic amines in the venoms act as the main pain-producing principles 46). The contents of these amines in the venom may affect the severity of pain production, edematous reaction of the skin, or increase in skin permeability by stings of these insects. Consequently these amines act as toxins for their defense, together with acetylcholine, enzymes, and peptides 47). 

The reduction of substituted 4-hydroxy-5,6-dihydropyrimidins such as VIII/ 114 is a reaction used several times as key step in the syntheses of polyamine alkaloids, Scheme VIII/21. In the presence of NaCNBH3/AcOH at 50°, ring enlarged azalactams of type VIII/115 are obtained in yields of about 90 %. Aza-lactams, prepared by this method, are nine- [65], thirteen- [66], and seventeen-membered [67] [68] [69]. 

This reaction was applied to the synthesis of the macrocyclic polyamine alkaloid celacinnine [65] a key step of this synthesis was the conversion of the bicyclic VIII/123 to nine-membered VIII/124, see Scheme VIII/23. 

Although selected polyamines, (VII), functionalized with guanidine, (VIII), were prepared by Dhal [4] for use in the treatment of gastrointestional disorders their application as a crosslinkable resin was also suggested by the author. 

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