Longmire and Simpson, who both exited their respective posts last year after more than a decade in charge, will almost certainly be sounded out by the Demons after they sacked Simon Goodwin on Monday night.
The former North Melbourne teammates have worked in the media this year, addressing the renewed interest in their coaching ability on Wednesday night.
"I've got two thoughts: One is I feel for 'Goody' (Goodwin)," former Sydney coach Longmire told Fox Footy's AFL 360.
"When you've been a coach, you've got great empathy for other coaches in those situations that Simon's found himself in.
"The second thought I've got is I can't be 100 per cent definitive on what the future holds."
Simpson insisted he had "refused" to entertain thinking about coaching again.
".. It's life changing," the West Coast premiership coach told Fox Footy.
"So to go through a process of ... to block out any type of thought, of contemplating getting back into coaching, you just refuse to think about it because you're dealing with what you're doing now."
Simpson threw up his former Eagles assistant coach Daniel Pratt, who now works at the Western Bulldogs, as a coach-in-waiting.
He said Pratt would be thinking "please ring me, I'm ready".
'Whereas we're (him and Longmire) not in that space.
"I'm having a glass of red tonight when I get back to my hotel room, I'm meeting a few mates for lunch tomorrow."
Earlier, Â Nathan Buckley saw coaching Melbourne as a "quite compelling" prospect but would need to be convinced to jump back into an AFL hot seat.
Former Collingwood coach Buckley has been touted as one of the most likely contenders for the vacant Demons job, along with Simpson and Longmire.
Buckley spent almost a decade in charge at Collingwood, leading the club to the 2018 grand final.
He departed midway through the 2021 season and has since taken up football commentary roles on television and radio.
"I would take the call," Buckley said on SEN on Wednesday when asked about a possible approach from Melbourne.
"I would have a chat but a lot would have to fall into place to leave this position of comfort I have found."
Buckley coached Collingwood in 218 games with a 54 per cent winning ratio, and said he still had a desire to coach at the top level.
"It's there, otherwise it would be an easy no," the 53-year-old said.
Buckley sees appeal in the Melbourne job, highlighting the playing talent currently on the club's list.
"I think the Melbourne prospect is quite compelling," he said.
"There's a lot that needs to settle. Big club, storied history.
"Experience in the playing group is unquestioned and I like their young group of players as well.
"In that sense, there is a compelling case there. But there's plenty of water to go under the bridge."
Leading assistant coaches Hayden Skipworth (Collingwood) and Steven King (Geelong) were among the contenders for the West Coast job last year, and could also be in Melbourne's sights.