People have been making toothpaste for quite a long time. The recent innovation has been fluoride, which is something of a game changer. Various recipes and abrasives have been tried by various civilizations, you'd need to specify for more detail.

If you're talking about prehistory, and I suspect you might be, that's a question anthropologists have been exploring for a while.

There's evidence that our hunter-gatherer ancestors tended to have much healthier teeth than we do, due mostly to their diets. This appears to have changed with the agricultural revolution, when we started having a lot more carbs in our diet. There's also evidence that we've been using toothpicks to clean our teeth and gums for over a million years.

If anyone has found evidence of prehistoric tooth paste, I'm unaware of it.