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Notes on Sync Services and Spotlight
Spotlight will index any cache files the Entourage daemon has created even if the Microsoft Database daemon is not launched, but no new cache files will be created until the daemon is launched again.
When Spotlight is turned on within Entourage, a series of files for indexing is created here:
The "cache" files represent a mirror of your Entourage database contents and then are picked up by and parsed by the Entourage Spotlight Importer when the OS' Spotlight indexing process is ready. When this processing occurs, depends on the OS. Entourage does not attempt to force Spotlight to index these items. The OS usually does this when it has some idle time.
It's similar to how a newly purchased song from the iTunes Music Store finds its way into your Spotlight search results. When you purchase a new song from iTunes, the song is saved as a file within your iTunes library. The OS takes note of the new song file. Whenever it gets some idle time, it hands the file off to a Spotlight importer specifically for music files. The importer reads the metadata (e.g. song title, author, etc.) from the file and tells this information to Spotlight. It's at this point that Spotlight is first able to allow you to search on this information.
In Entourage's case, the OS takes note of all these new files, eventually handing them off one-by-one to the Entourage Importer. The importer reads each file, finds information such as an e-mail's subject, an event's due date, or a contact's category, and then provides all such metadata to Spotlight. At this point, the Entourage files and their metadata should be searchable within Spotlight.
Typically this happens pretty fast, but if you're doing a lot on your computer, it may take some time. If you've got lots of items in your Entourage database, there will be large numbers of these files created the first time you turn on Spotlight--so it might take some time. After which, it'll be just as fast (if not faster) as the time it takes for a new song to show up in your Spotlight results.
More info: Entourage 2008 & Spotlight