De-Saturation Mask Not Working... Exactly

Hey guys... weird problem... I am trying to create one of those images where you desaturate all the color out of an image and leave only a few select "highlight" components in color for effect...  so I go to the layer, click on the "Create new fill or adjustment layer" button at the bottom of the layers panel (next to create mask), and use the Hue/Saturation option, then desaturate the setting, then paint bucket the layer to black, and then use a white brush to wipe out the colors in the areas that I want.  It seems like it does it fine, but the thing is, it doesnt desaturate 100%.  This has happened in another "desaturate" process (cant remember what it was exactly).  It seems to take out the color but there is still definitely some brownish or whatever hue in there.. it shows as such when I use an eyedropper to check the "new color," and when I turn the image into grayscale, it defintely is different.
So why can tthe white brush desaturate the colors 100%  There must be some other setting I am missing?
Thanks!

If the image should be for web you should switch to RGB anyway.
I edited the previous message, so you may have missed this:
Another option would be to manually create a 4C-black with Curves and Channel Mixer Adjustment Layer(s).
Basically I recommend you consider doing the correction in RGB and then separate ideally with a profile with a fairly strong GCR.
But you are right that one can get quite a way without understanding everything Photoshop does … and who can claim to do anyway? (apart from some Adobe employees …) 

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