Mountain Lion Mail addressing

I have 3 email accounts which I handle within Mail (business, private and signup): my default addresss within Mail is my business one; this means if I forget to select my private email address instead of my default one (as if I would do such a stiupid thing ....) a private email goes out to a private contact, which is annoying all round

I'd like to configure Mail to use one of my 2 non-default accounts (e.g. private instead of business) if I have selected a known contact/email address when starting the email for a known contact.

Is this possible?