When the Romans occupied the Middle East. approximately 50 bc
true in a way
& yet the Romans didnt actually use the word palestine at all but rather only palaestina & to a lesser extent philistia
& indeed if you arent really asking about the exact word palestine
but are actually also interested in any similar but older words that gave rise to the word palestine then you would have to go back a few centuries earlier than the Romans to the ancient greek word for both palestine & palaestina
which was palaistine
& indeed even a few centuries before that
the ancient Hebrew word for all the above
was already pelesheth or plesheth
but even pelesheth has similar variations in possibly earlier languages
such as akkadian & Egyptian
not to mention the language of the ancient palestinians themselves
in which the word most likely truly originated
albeit in some form that is unknown today
as their name for their homeland itself
or for themselves its people
when they first arrived there some 3200 years ago
if not earlier
but on the other hand
if you really mean the word palestine itself
& will accept no substitutes or ancestors or other near misses
then i have to tell you that palestine itself per se was in fact not widely used if at all in English until the 20th century
indeed it was only revived as a political territorial name in 1920 for the british mandate for palestine
i say revived because the word hadnt really been used much in any form to mean a real living place since the crusades
nineteenth century English much preferred the alternative form of the word
which was & still is philistine
so i think the truest available answers for your question are either shortly before 1920 or else about 1200 bc
depending entirely on what you yourself mean & would perhaps like the answer to be
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