From the linden flower to linden honey--volatile constituents of linden nectar, the extract of bee-stomach and ripe honey.

Honey is produced by honeybees (Apis mellifera), which collect nectar from flowers, digest it in their bodies, and deposit it in honeycombs, where it develops into ripe honey. We studied the evolution of the volatile constituents from the nectar of linden blossoms (Tilia cordata) to honey via the 'intermediate' honeybee. The sampling of the contents of the honey stomach or honey sack of the bee is unique. Extracts were prepared from nectar, from the liquid of the honey stomach, and from ripe honey. The chemistry is extremely complex, and compounds spanning from monoterpenes (hydrocarbons, ethers, aldehydes, acids, and bifunctional derivatives), isoprenoids, aromatic compounds (phenylpropanoids, phenols), and products degraded from fatty acids to alkaloids, were identified. Some compounds definitely stem from the plants, whereas other interesting constituents can be attributed to animal origin. Two derivatives of decanoic acid, 9-oxodec-2-enoic acid (12) and 9-hydroxydec-2-enoic acid, identified in the honey are known to be constituents of the so-called 'Queen's pheromone'. Two metabolites of these acids were identified in the extract of the honey stomach: 8-oxononanal (10), a new natural product, and 8-oxononanol (11). There structures were confirmed by synthesis. Nectar and honey stomach contain many aldehydes, which, due to the highly oxidative atmosphere in the honeycomb, are found as corresponding acids in the honey. Two acids were newly identified as 4-isopropenylcyclohexa-1,3-diene-1-carboxylic acid (14) and 4-(1-hydroxy-1-methylethyl)-cyclohexa-1,3-diene-1-carboxylic acid (15).