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West and South towards Gualeguaychu, Victoria, Rosario, Buenos Aires
Walk out of town to the Ruta 135 towards the Ruta 14. That's a major crossing, so only get into a car if it's driving at least 15 kilometers on the Ruta 14 south, as you'll pass a good gas station. Asking for at least Concepcion del Uruguay (it's in Argentina) is best, you can switch directions onto the Ruta 39 from there to go west towards Rosario, or continue on the 14 south towards Buenos Aires.
West and North towards Posadas
Follow the same advice as above, but DO get out at that crossing with the Ruta 14. There's a Shell gas station you can enter via the tiny roundabout and then catch a ride on the main road.
Go again to the main road Ruta 135, but hitchhike east towards the border. There's an YPF gas station in this direction 4km from this crossing that you can use to ask people directly to take you across the border.