Jiraiya, his senses honed by years of dealing with the opposite sex, knew an angry woman when he saw one. He just had the unfortunate inability to comprehend the difference between, 'I'm annoyed, please bother me until I'm un-annoyed' and 'I'm going to kill you until you're dead and you die' until he was attacked.
"Is there anything I can do to help fix things? I'll pound the douche bag," he thumbed over his shoulder, "for you if you want." Ladies always loved a big strong man taking out their revenge for them!