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Everything you need to create your own html TOC is found in the "toc.ncx" file in the epub itself. You don't have to go chasing down temporary files and such. I've done it myself in the days before the facility was added to calibre or sigil. As long as you're poking around in the toc.ncx, you can also create navigation links to the next or previous chapters, or up to the top to the html TOC. I've done that, too.
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