The restricted distributions of some classes of secondary metabolites in the angiosperms make them valuable taxonomic characters in assessing systematic relationships at higher levels of classification. Yet, for several reasons, secondary metabolites have not, until recently, been widely used as taxonomic characters above the family level. In this paper, the distributions of a number of classes of secondary compounds are discussed with reference to four recently published systems of higher angiosperm classification: Cronquist's of 1981, Dahlgren's of 1980, Takhtajan's of 1980 and Thome's of 1981. Some of the problems faced in choosing and using secondary metabolite data for systematic purposes (including the effects of our increasing understanding of their functional significance) are covered as well. Among the classes of secondary compounds treated here, benzylisoquinoline alkaloids, iridoids and be–talains are shown to be the most important systematic markers used at present at higher levels of classification, although glucosinolates, polyacetylenes and some other types of alkaloids are also demonstrated to be valuable criteria for making taxonomic judgments above the family rank. In addition, certain terpenoids, flavonoids, phenolics, cyanogenic glycosides and non–protein amino acids are illustrated to be of systematic use in particular ca
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