zene (Ph-I==O)/manganese tetraphenylporphyrin (TPPMn) as the oxidant (48). An aqueous system, containing huminic acids and traces of Cu(I) (49), gives similar results (50). Since these abiotic degradations can be carried out on a gram scale, the by-products shown in Figure 8 become available as pure compounds after extensive chromatographic separations. Up to now, more than 20 individual compounds have been characterized (50). Their structures fit into a general scheme of an oxidative sequence starting with a pentadienyl radical as depicted in Figure 9. Once generated, the radical reacts at all possible positions with oxygen and yields the three isomeric alcohols as the primary products. Further oxidation of the alcohols provides the dihydrotropones, which were first isolated from the two brown algae Dictyopteris australis and Dictyopteris plagiogramma (28, 51). Elimination of water generates the alkyltropilidenes. If singlet oxygen is involved, the corresponding hydroperoxides will be formed. Their subsequent decomposition may be responsible for the formation of the ketoepoxide and for the fragmentation of the carbon framework. The isomeric butylbenzaldehydes and the substituted furane fit into the same reaction channel. The butylbenzenes result from decarbonylation of the alkylbenzaldehydes. Butylbenzene and the alkyltropilidenes are remarkably attractive for male gametes of E. siliculosus; the alcohols and ketones are not. Owing to their ability to act as Michael acceptors, the dihydrotropones and tropones, which represent the major degradation products of the cycloheptadienes, may be important as chemical defenses (e.g., feeding deterrents) of those brown algae that are capable of synthesizing them. Similar degradative routes can be expected for all the other C11 hydrocarbons, and it seems likely that chemical model systems like Ph-I==O/TPPMn can provide all the required reference substances.
Exploratory experiments with dictyotene and suspensions of male gametes of E. siliculosus showed a significantly enhanced production of the 6-butylcyclohepta-2,4-dienol and its isomers. This indicates that a biological degradative pathway does exist and that this pathway follows the same oxidative sequence as the abiotic route. However, final conclusions about the biotic contribution to the pheromone transformation cannot be drawn before careful analysis of the degree of enantioselectivity of the biotic reaction.
Female gametes of marine brown algae release and/or attract their conspecific males by chemical signals. The majority of these compounds are unsaturated, nonfunctionalized acyclic, and/or alicyclic C11 hydrocarbons. Threshold concentrations for release and attraction are generally