Do NOT boil vinyl tubing. Only boil silicone tubing, since it's made to withstand those temperatures. I don't even use vinyl to drain my mash tun (silicone all the way). Once things are chilled, vinyl is good/safe...
Zeppman, you can try oxyfree and a good StarSan soak for the ancient tubing. Personally, unless you have no other option, I would delay the brewing until you've replaced that aged tubing.
Whenever a blow-off tube, racking tubing, or any other vinyl tubing looks questionable, or has an odor to it (I'm rather sensitive to bad smells, so I probably detect them earlier) I toss it and go with new. I typically check out any tubing I'll be using at least a day or two before the brew day, leaving me more than enough time to get replacements from the LHBS. That is, IF I don't have more on hand already. I make it a practice to have 5-10' of racking tubing on hand at all times. When I go to the LHBS (which isn't too far from where I live) and I know I don't have more than 5' in reserve, I get more. It's so bloody cheap (per foot) that [IMO] it's silly to not have some on hand.
I also make sure to have extra silicone tubing on hand. Right now I have about 10' of 1/2" ID silicone tubing in reserve. Mostly because my system isn't in a final form, so I never know when I'll need to cut a length to use.
BTW, I received some items that the person who had them before would boil to 'clean' them... Let me tell you, a couple of hour soak in PBW had a LOT of stuff coming out of them... IF you plan to 'clean' via a boil, also include a scrubbing with that, while hot, and then put the items back in for some more time. But, if you don't feel like dealing with 212F+ items, just mix up a batch of PBW with hot tap water and give them a soak. I would also include a scrubbing of the items, and another soak if needed.