You can get there in less than 15 hours if you leave at
4:33 am to Frankfurt arr. 8:44/dep. 9:01 to Paris Est - arrive at 12:49, take the Metro to Montparnasse station in Paris, then the TGV train to Toulouse, dep. 14:10/arr. 19:22.
Or you could take a number of other combinations that take between 15 and 19 hours with changes.
One comfortable combo is the night train from Berlin to Paris,
dep. 21:34/arr. Paris Nord 9:14, then the Metro to Paris Austerlitz, and from there to Toulouse dep. Paris at 10:17; arr. 16:33.
http://www.oebb.at/en
For toulouse, choose "Toulouse-Matabiau"
That's the main station.
You can probably fly more cheaply, like on germanwings from Berlin to Bordeaux, then a train from Bordeaux to Toulouse..
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