Some ideas you might try:
You could hook into the order.php class and replace the following code with code that writes something to your other database:
PHP Code:
/* START: ADD MY CUSTOM DETAILS
* 1. calculate/prepare custom information to be added to this product entry in order-confirmation.
* 2. Add that data to the $this->products_ordered_attributes variable, using this sort of format:
* $this->products_ordered_attributes .= {INSERT CUSTOM INFORMATION HERE};
*/
$this->products_ordered_attributes .= ''; // $custom_insertable_text;
/* END: ADD MY CUSTOM DETAILS */
Or you could hook either of these notifier points using the observer/notifier system:
NOTIFY_ORDER_DURING_CREATE_ADD_PRODUCTS
NOTIFY_CHECKOUT_PROCESS_AFTER_ORDER_CREATE_ADD_PRODUCTS