The en- in enemy is a prefix meaning "not": the origin is Latin inimicus, from in- + amicus — a "not friend" or an "unfriend" (Online Etymology Dictionary—enemy).
The Latin in- changed to en- when the word passed through French and into English. Compare enmity, which keeps the en- form, and inimical, which is the same origin, but uses in-. I assume the difference here is the difference in their relative dates of entry into English. The Online Etymology Dictionary dates enemy to early 13c. and inimical to the 1640s.
In the entry for in-, the Online Etymology Dictionary notes:
In Old French and Middle English often en-, but most of these forms have not survived in Modern English, and the few that do (enemy, for instance) no longer are felt as negative. The rule of thumb in English has been to use in- with obviously Latin elements, un- with native or nativized ones.
By "these forms have not survived", does this mean the prefixes were changed to in-, or have these words disappeared altogether? Why did this change occur? Are there any other examples of the en- form surviving as a negative prefix besides enemy and enmity?
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