From Middle English when, whanne, from Old English hwenne, hwænne, hwonne, from Proto-West Germanic *hwannē, from Proto-West Germanic *hwan, from Proto-Germanic *hwan ("at what time, when"), from Proto-Indo-European *kʷis ("interrogative base").
Cognate with Dutch wanneer ("when") and wen, Low German wannehr ("when"), wann and wenn, German wann ("when") and wenn, Gothic 𐍈𐌰𐌽 ("when, how"), Latin quandō ("when"). More at who.
Interjection sense: a playful misunderstanding of "say when" (i.e. say something / speak up when you want me to stop) as "say [the word] when".
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