Let .<ext> be the extension you want to deassociate.
With a registry editor (e.g. regedit.exe),
1. go to
HKEY_CURRENT_USER\Software\Microsoft\Windows\CurrentVersion\Explorer\FileExts\
remove the subtree .<ext>
2. go to
HKEY_CLASSES_ROOT\
remove the subtree .<ext>
remove the subtree <ext>_auto_file
This cannot be done directly in Windows, but... there are alternatives like
http://www.winhelponline.com/downloadattachment.php?
aId=9f390841cdbe0c2457898179b80dfce0&articleId=231
or
http://www.creativelement.com/powertools/#download