I'm thinking about creating a DOS 6.22 bootable CD with the whole of the OS installed for utility/legacy/support work, how would one go about this? What I was going to do was create a bootable DOS diskette and burn it to CD as a floppy emulation and then burn the rest of the DOS directory from another location to the same CD. Would this work or is there a better way to do it? I've tried searching the net but some of the hits are a bit ambiguous in details.

Should work fine, but there really isn't any need for a full install. Just create a bootable CD from an image of a startup floppy disk and copy the needed utilities to a separate folder. Be sure to include mscdex.exe and a driver for your CD-ROM such as oakcdrom.sys so you'll be able to access your other folders on the CD. Make sure you use 8.3 file names for your files and folders that you'll be accessing from DOS. You can have other folders for Windows stuff with long file names.

Personally I would suggest using a newer version of DOS since 6.22 does not support FAT32 partitions among other things. Instead I would use MS-DOS 7 for example and copy the utilities from the Windows 98 Commands folder. You could also add third party DOS based utilities such as a memory diagnostic or a utility to read NTFS partitions. There will be a lot of room left over of course, so I'd fill the rest with updates for different versions of Windows, updated drivers, utilities for Windows, and anything else you frequently use in your work.