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Pretty sure that his parents were at least suspicious of Itachi, judging by the way things were after the police tried to arrest him. Also, Itachi's father always told Sasuke to grow up to be like his big brother but when Itachi's behavior changed he told Sasuke not to become like Itachi. When Itachi came to kill them they put 2 & 2 together and realized he was working for Konoha.
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