This table on Wikipedia says the inequality symbols were first used in 1631[1]. However guillemets (« ») date to the mid sixteenth century[2] and are still used as quotation marks in many languages. Although according to the page about brackets[3], chevrons were the earliest form of brackets, however I couldn’t find a year.

1: https://en.wikipedia.org/wiki/Table_of_mathematical_symbols_...

2: https://en.wikipedia.org/wiki/Guillemet

3: https://en.wikipedia.org/wiki/Bracket#History