Lots of caramel malts have toffee flavor...especially in the C-60 to 120 range. This is easily done since caramel malts don't have to be mashed.
There's also kettle caramelization. If all grain, you can take a gallon or so of first runnings and boil it down to a more concentrated, syrupy liquid, then sparge and go on as normal. Same basic idea with extract, but be careful not to scorch it. Also, you can create your own caramel by simply melting cane sugar at a medium heat, stirring nigh on to constantly. It will do nothing for what seems like forever, then very, very quickly go from white to tan and caramelly to dark and richly caramelly and toffee-like to burned, so watch it closely. Keep in mind it will continue to darken a bit after heat is removed, and when you add that syrup to your boil it will seriously bubble up (it's hotter than boiling liquid). Done right, you can get a decent toffee flavor that way as well.
I think that Kentucky Bourbon Barrel Ale just nail a great toffee flavor. I wonder if they have anything on their website or would respond to an email.
Just did precisely this on a 2-row/fuggles smash. Between the first runnings and the rest of the wort, total boil time was about three hours. We can either blame or credit Sgt Stogie for the results. / It's conditioning now. The young beer tasted good.
Im going to have to try this technique out for sure. Thank you both for the advice on this. I think it would be a good way to infuse a heavy flavor into a beer in order to get them to stand out as opposed to getting lost in the beer.
And KBA's response: Hey Chris, The sweetness such as toffee and caramel we get in our Kentucky Bourbon Barrel is actually all from the aging process. We start with a lighter base ale (Kentucky Ale), that allows that sweetness in only 6 weeks of aging in temperature controlled environment. Hope this helps! Cheers, Nate