Carlos Aray Ejecutivo has buses to Quito ($14, 10 hours) at 5:05am, 9:15am and 7pm via Jipijapa, Portoviejo, Chone and Santo Domingo. Alternatively, you can catch the bus to Portoviejo or Manta to make connections.
Reina de Camino has the comfiest service to Quito ($14, 10 hours), with one first-class bus at 8pm.
To South Coast
Cooperativa Manglaralto has buses heading to Santa Elena ($4, 1½ hours) every 20 minutes from 4am to 7pm, stopping in Montañita ($2.50).