When two individual thoughts in a sentence contradict each other.
Example: "John wants cookies but I want ice cream."
You can also use 'but' at the start of an past unreal conditional sentence (3rd conditional to some) to place blame on someone or identify responsibility e.g. 'But for John, I would have been killed' means that something John did stopped me from being killed. Or 'But for Dave, we wouldn't have been late' means that Dave did something that made us late.
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So- you are asking when to use 'when' in a sentence. When you are asking how to use when in a question, you are already using when in a sentence, because a question actually is a sentence. I like to use when in a sentence whenever I like.
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Use it in a big sentence.