FR 4596 then W6 4406 at Barcelona
Porto → Barcelona → Sofia
Timetable, Barcelona time
22:15FR 4596 from Porto at the gate
19:40W6 4406 to Sofia leaves the gate
21 h 25 apart on the timetable, overnight
W6 4406 leaves 21 h 25 after FR 4596 arrives on the timetable: more than half a day, so not a connection we count.