You can't unmount a filesystem if it is in use. It is in use if you (or someone else) has cd'd into it or if there is a process running from that filesystem.
Make sure no one has cd'd into the filesystem. If everyone is out and you still cannot cd into it, try to determine what the process is that is running from the filesystem. You can run fuser -fu /<filesystem> to see who is running the process and what the pid is. Then kill the process if possible.
In addition, if you have a two-tier filesystem layout (for example, /main, /main/data, /main/index, /main/rbs), you aren't going to be able to unmount /main until /main/data, /main/index, and /main/rbs are unmounted.