Alvaro Morata's late goal earned Spain a 1-0 win in Portugal and the last place in the UEFA Nations League finals on Tuesday, while the Czech Republic was relegated from the top tier after losing in Switzerland.
Portugal, winner of the inaugural Nations League in 2019, needed just a point in Braga to finish top of Group A2 but dropped to second as Morata tapped in Nico Williams' header on 88 minutes.
"When we had to stand up, we did," Morata told TVE. "If we had lost, it had to be giving everything we had on the pitch, and that's what we did."
Spain joins the Netherlands, Italy and Croatia in the finals which are scheduled for June next year.
Switzerland, who beat Spain 2-1 in Zaragoza on Saturday, was indebted to goalkeeper Yann Sommer as he saved a second-half penalty to preserve victory over the Czechs.
Remo Freuler and Breel Embolo scored within a minute of each other in the first half in St Gallen, but Patrik Schick pulled one back before the break.
Schick saw his second-half penalty kept out by Sommer as the Swiss won 2-1, condemning the Czech Republic to relegation to League B.
Scotland clinched promotion to League A after a 0-0 draw against Ukraine in Krakow, having beaten the same opponent 3-0 last week in Glasgow.
"We don't want to stop, we want to keep getting better," said Scotland coach Steve Clarke.
"These players are desperate to do well for their country and they have had a great week."
Robbie Brady's stoppage-time penalty gave the Republic of Ireland a 3-2 victory over Armenia in Dublin in the other game in Group B1.
Irish captain John Egan and Michael Obafemi put the host two goals in front but Armenia equalized as Artak Dashyan and Eduard Spertsyan struck in quick succession.
Dashyan and Hovhannes Hambartsumyan were sent off to leave Armenia with nine players as Brady's winner saw the Irish finish third in the section.
Serbia took top spot in Group B above Norway as forward pair Dusan Vlahovic and Aleksandar Mitrovic got the goals in a 2-0 victory in Oslo.
Mitrovic's strike was his 50th at the international level. He scored a hat trick in Saturday's 4-1 win over Sweden.
Sweden will drop into League C after a 1-1 draw with Slovenia in Solna, where Emil Forsberg canceled out Benjamin Sesko's opener for the visitors.
Greece made it five wins from six in Group C2 as it beat Northern Ireland 3-1 in Athens. Kosovo thrashed Cyprus 5-1 in Pristina.
Brazil smashes Tunisia
Brazil went fire blazing through 10-man Tunisia, netting five and conceding one in a friendly on Tuesday with Raphinha scoring twice and setting up another goal in their last game before the World Cup.
It was another dominant performance by the Samba boys who beat Ghana 3-0 on Friday, giving their fans plenty of reasons to be excited by their young team heading into Qatar where they will bid for a record-extending sixth world title.
Raphinha opened the scoring in the 11th minute with a brilliant header from the edge of the area over goalkeeper Aymen Dahmen. However, Tunisia equalized seven minutes later with an opportunistic header by Montassar Talbi from a free kick.
Brazil was back in front a minute later though when Raphinha found Richarlison ghosting behind the defense and the striker fired a low shot between the keeper's legs.
During the goal celebrations a banana was thrown from the stands toward the Brazil players, who have been vocal against racism after Vinicius Jr was racially abused by Atletico Madrid fans before their derby against Real Madrid this month.
The Brazilian FA (CBF) released a statement "vehemently repudiating yet another episode of racism in football."
"The fight against racism is not a cause, but a fundamental change to wipe this type of crime from the planet. I insist on saying that the punishments need to be more severe," Brazilian FA president Ednaldo Rodrigues said.
Richarlison said racism would continue if there was no punishment handed out.
"As long as they keep 'blah blah blah' and don't punish, it's going to continue like this, happening every day and in every corner," he added.
Brazil extended its lead through a Neymar penalty in the 29th minute after Aissa Laidouni held Casemiro back.
Raphinha scored his second with a precise low shot from the edge of the area in the 40th after a lightning counterattack.
Two minutes later, Tunisia defender Dylan Bronn received a straight red card for a foul on Neymar.
With victory assured, Brazil eased off in the second half as manager Tite sent on several substitutes.
Flamengo forward Pedro, the biggest sensation in the Brazilian league this season, came on and netted the fifth with a superb first-time shot from the edge of the box in the 74th.
Brazil will open their World Cup campaign against Serbia on Nov. 24 and also face Switzerland and Cameroon in Group G.
Uruguay overpowers Canada
Uruguay beat Canada 2-0 in their final friendly before the World Cup with Nicolas de la Cruz and Darwin Nunez scoring first-half goals to give the South American side victory in Bratislava on Tuesday.
De la Cruz opened the scoring in the sixth minute with a sublime free kick that curled over the wall and beat the keeper.
Liverpool's 75 million euros ($71.86 million) forward Nunez doubled Uruguay's lead just after the half-hour mark when he powered home a header after his strike partner Luis Suarez floated in a cross.
Canada had more possession and did threaten but John Herdman's side struggled to find the final ball as Uruguay kept a clean sheet and returned to winning ways following their 1-0 loss to Iran last week.
Canada is in Group F along with Belgium, Morocco and Croatia while Uruguay faces Portugal, Ghana and South Korea in Group H at the World Cup, which kicks off on Nov. 20 in Qatar.