i dont know wat rain nin ur talking about but if its zabuza its in naruto episode 6
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after the chunin exam To be a little more specific, Naruto encounters Gaara episode 77 Light vs. Dark: The Two Faces of Garra. They don't start fighting until, 78-80, naruto's Ninja Handbook.
Its naruto shippuden episode 139.
Naruto Episode 134: The End of Tears
Hiruko appears only in naruto shippuden movie 3. Not in episodes.
In episodes 166-169