Internacional, which also won the 2006 Club World Championship, was edged out by Nacional of Uruguay on goal difference for second place in Group 4 despite beating the Montevideo team, 1-0, on Thursday.
River Plate, winner of two Libertadores Cup titles, finished behind Colo Colo of Chile and Venezuela's Caracas FC -- which it amazingly lost to twice.
Gremio must beat Paraguay's Cerro Porteno at home on Tuesday to go through from Group 3. Cerro, Tolima of Colombia and Gremio all have seven points after five games, but Gremio trails on goal difference. Colombian champion Cucuta is one point behind but would go through if it won at Tolima the same evening.
In Group 7, Boca must beat last-place Bolivar of Bolivia by two goals at home on Thursday to be certain of qualifying. The winner of Toluca of Mexico and Cienciano of Peru, which meet the same evening in Toluca, will go through. Both teams would also advance if they tie and Boca fails to win or beats Bolivar by only one goal.
Brazilian champion Sao Paulo, winner of three Libertadores Cups, most recently in 2005, is in better shape to advance. It is tied for first place in Group 3 with Audax Italiano but leads on goal difference and would go through with a draw when it hosts the Chilean outsider on Wednesday. Mexico's Necaxa, one point behind in third place, needs a win at home against Peruvian champion Alianza Lima, who has lost all five games so far.
Of the 10 teams to advance to the round of 16, only Santos of Brazil finished with six wins in six games.
Group 1 (final): 1. Libertad (Para.) 13 points; 2. Club America (Mex.) 12; Banfield (Arg.) 9; El Nacional (Ecua.) 1.
Group 2 (one game to play): 1. Sao Paulo (Brazil), Audax Italiano (Chile) 10 points; 3. Necaxa (Mex.) 9; Alianza Lima (Peru) 0.
Group 3 (one game to play): 1. Cerro Porteno (Para.), Tolima (Col.), Gremio (Brazil) 7 points; 4. Cucuta (Col.) 6.
Group 4 (final): 1. Velez Sarsfield 11 points; 2. Nacional (Uru.) (5-4) 10; 3. Internacional (7-7) 10; 4. Emelec (Ecua.) 3.
Group 5 (final): 1. Flamengo (Brazil), 16 points; 2. Parana (Brazil) 9; 3. Real Potosi (Bol.) 6; 4. Maracaibo (Vene.) 2.
Group 6 (one game to play): 1. Colo Colo (Chile), FC Caracas (Vene.) 9 points; 3. River Plate (Arg.), LDU Quito (Ecua.) 5.
Group 7 (one game to play): 1. Cienciano (Peru), Toluca (Mex.) 9 points; 3. Boca Juniors (Arg.) 7; Bolivar (Bol.) 4.
Group 8 (final): 1. Santos (Brazil) 18 points; 2. Defensor Sporting (Uru.) (8-7) 9; 3. Gimnasia y Esgrima (Arg.) 9 (9-10); 4. Pasto (Col.) 0.
(Teams that have clinched are in bold.)