This is one of my favourite scenes in Mad Men. Matthew Weiner does a great job with choosing music for the show. Rarely do big sixties hits receive airplay, but when they do they make a great impact.
The Rolling Stone’s “Satisfaction” matches this scene perfectly. Just as Don Draper sparks up his cigarette while wearing his pristine white shirt you hear Mick Jagger sing:

When I’m watchin’ my T.V.
And that man comes on to tell me
How white my shirts can be
But he can’t be a man ‘cause he doesn’t smoke
The same cigarrettes as me
I can’t get no, oh no, no, no
Hey hey hey, that’s what I say