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In this case it is a banana cream pie, but also in candies. The simple argument I've heard is that the alcohol in it will boil off, but in my case my imitation vanilla doesn't even contain alcohol. (Uses propylene glycol, not really an alcohol, right?)

But either way, why would we care about the alcohol boiling off. It's the vanilla flavor we want right? Does cooking it affect the flavor? (Cakes and such seems to counter that thought) are these recipes just misguided?

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It's not the alcohol specifically - the reason alcohol is used to make extract is not because it contributes any flavor itself, but because it dissolves specific desirable substances from the vanilla pod. When the alcohol boils off (or whatever solvent is used in the artificial flavoring), you will also lose some proportion of the flavoring compounds dissolved in the extract.

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But why would the alcohol evaporating take the flavor with it? When salt water evaporates, the salt doesn't go with it. That's how they purify water/alcohol. By distill ing it to leave behind the other elements. Do the chemicals that compose the actual vanilla flavor evaporate so easily? –  Eric G Nov 28 '13 at 21:10
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Because the flavoring compounds are volatile, unlike salt. (Or at least I assume so - I don't have any specific knowledge of vanilla chemistry.) –  user5561 Nov 29 '13 at 4:09

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