Liverpool's Philippe Coutinho has submitted a transfer request that has been rejected by the club, Press Association Sport understands.
The Brazil playmaker has been targeted by Barcelona, whose bid of about PS90 million ($148m) was rebuffed by Liverpool on Wednesday.
It is understood Coutinho - who is out of Saturday's Premier League clash with Watford because of a back problem - declared his desire to leave the Merseyside club on Friday by submitting a transfer request via email. The request was turned down.
That news emerged only hours after Liverpool's owners had issued a statement stressing their stance that the 25-year-old would not be sold during the current transfer window.
Barca, who sold Neymar to Paris St Germain last week for a world-record $332m, made their offer on Wednesday having already had a PS72m bid for Coutinho turned down in July.
Liverpool boss Jurgen Klopp has gone on record a number of times emphasising the player is not for sale.
The club's owners, Fenway Sports Group (FSG), backed that up on Friday morning in a statement:
''The club's definitive stance is that no offers for Philippe will be considered and he will remain a member of Liverpool Football Club when the summer (transfer) window closes," it read.
That message appeared on Liverpool's official website just prior to Klopp speaking at a press conference, during which he said of FSG's statement: ''I think if somebody, in this case FSG, is saying something like this, that is the statement.
''I have said what the club's decision is about this and now you can read it - that is maybe the only difference. And that is the way it will go."
Soon after the press conference, reports emerged that Coutinho had handed in a transfer request. Liverpool initially insisted that was not the case, but it is understood the player did send an email.