The First Minister was responding to fast-moving events on the continent as Theresa May tries to persuade the European Union to grant the UK a further deadline extension to avoid leaving the bloc with no deal.
European leaders will meet on Wednesday evening for an emergency summit in Brussels to decide whether to offer the UK another delay to Brexit.
Mrs May wants to postpone the UK’s exit until 30 June but the EU is expected to offer a longer delay.
Earlier, the SNP leader tweeted: “Tonight, 12 of the 27 EU member states that will decide the UK’s future have populations smaller than or similar in size to Scotland’s. If we become independent we get to sit at that table - enjoying the same solidarity shown to Ireland - instead of being sidelined by Westminster.”
One political writer observed on Twitter: “It says something about the power dynamics now at play in British diplomacy that should they choose theoretically tiny Luxembourg, Cyprus or Malta alone could plunge the UK into chaos today.”
The First Minister responded: “It is gloriously ironic that #Brexit has ended up illustrating so powerfully the benefits for small countries of independence in Europe.”
The idea of an independent Scotland joining the EU has been a cornerstone of SNP policy for three decades.
Alex Salmond and his supporters pushed the party to embrace a more pro-European stance following his election as leader in 1990.
“Scotland will have open borders with England,” the SNP manifesto for the 1997 general election claimed. “European countries have abolished internal frontiers and our close family and trading ties with England will not be interrupted in any way by Scottish independence.”
This remained one of the party’s core messages on independence up to and including the 2014 referendum.
Following Brexit, pro-Union parties have regularly claimed that independence would now lead to a hard border between Scotland and England.