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It doesn't happen in the anime but it happens in the manga I'm not sure which chapter though.
Grimmjow appears during Arrancar arc. In the manga he makes his first appearance in chapter 198 and in the anime episode 116.
Envy first appears Chapter 6 (manga) , Episode 2 (2003 anime) and Episode 5 (2009 anime) .
Bleach chapter -15.
Wolfwood first shows up in Volume 3 chapter 18