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B&N is the plugin that supports TOC downloading and yes it merges it into the comments.
As to the why - (1) there is no separate field for TOC in calibre, (2) it is not possible to download into a custom column from a metadata download plugin, and (3) I would suggest "most" users store fiction in their libraries, for which a TOC is irrelevant which is why it is not a "standard" field.
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