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No best answer has yet been selected by GuavaHalf. Once a best answer has been selected, it will be shown here.
For more on marking an answer as the "Best Answer", please visit our FAQ.In Old English, 'who' was 'hwa'. A similar sound existed in Scotland for a long time after - indeed, there are many Scots who still pronounce it thus. You see it, with the spelling slightly modified, in the old song: "Scots wha ha'e wi' Wallace bled". As regards the modern English proninciation, that is simply one of the multitude of sound-changes that have affected language over time...hence, the 'oo' effect.
In Old English, 'why' was 'hwi'. Even in the Old Indo-European language, it was 'chwi', with the 'ch' as in Johann Sebastian Bach. Again the sound-change is just another of the endless variations that have occurred over time.