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Trying to home school older children with a preschooler is around is tough, as the preschooler naturally believes the world revolves around them, and until they learn to respect school time they're going to be a menace to your other students' learning environment.
A good tip to prevent your teaching from getting derailed by your active toddler is to be organized and have a number of distracting activities available for him or her. Set out lots of paper and crayons. Keep your Tupperware in a cabinet your preschooler can reach and go at it. An electronic educational toy that lights up and makes noises can keep a young one occupied for a long time, and give you the time you need to teach your elder students.
The trick is to keep a varied set of activities around so your toddler doesn't get bored too soon and come back to you seeking attention.