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Orochimaru isn't so much as evil as just someone with no morals who does whatever he wants. Right now letting Madara win is going to ruin his long term goals so that's why he's going to help the alliance. Once Madara is removed there's probably nobody who is capable of beating him anyways, especially since he's seemingly immortal.
Also, he's probably going to enjoy seeing Tsunade's response to him helping her.
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