"make estranged" (in feelings or affections), 1540s, from Latin alienatus, past participle of alienare "to make another's, part with; estrange, set at variance," from alienus "of or belonging to another person or place," from alius "another, other, different," from PIE root *al- (1) "beyond." Related: Alienated; alienating.
In Middle English the verb was simply alien "to estrange from," late 14c., from Old French aliener and directly from Latin alienare.