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目薬 is pronounced 'めぐすり' while 薬 'くすり'.
The pronunciation of '薬' change from 'くすり' to 'ぐすり'. What's the rule behind this change?

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This is rendaku (連濁) which commonly occurs in compounds in Japanese. Unfortunately, in general whether it applies or not isn't at all predictable. However, there are tendencies including the well-known Lyman's law which at least tells you where it cannot occur.

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