Latest versions of Windows do not have a boot.ini file. Instead, you must edit it under administrator using bcdedit in the command prompt. There is a steep learning curve when using bcdedit, and make sure to backup your current settings as you are messing directly with the registry.
Here is a quick tutorial on editing with bcdedit:BCDedit
Easy BCD simplifies all of this for you. Works with Linux and Mac also!
Windows, Linux, Mac, & BSD! Boot both from and into USB drives, ISO images, virtual disks, and more.
Create bootable USB sticks with repair utilities that you can take with you anywhere.
Protect against disaster.
Create entries to boot into recovery utilities or safe mode to prepare for a rainy day.
Add, rename, remove, configure, and reorder entries at whim.
Solve difficult problems.
Use EasyBCD to troubleshoot Windows, back up and repair the bootloader, and more.
Powerful scripting with NeoGrub
You’ll have the power to hide partitions, change active flags, and create complex boot scenarios.