The super PAC had initially invested $130 million to reserve time for broadcast and digital ads that would start running the day after the California and New Jersey primaries in June. But it decided to add an additional buy to accelerate the time line, aiming to sow early doubts about Mr. Trump, particularly among female voters who will have a disproportionate effect on the fall election and with whom Mr. Trump has shown a particular weakness in polls.

Female voters favored Mrs. Clinton over Mr. Trump, 55 percent to 35 percent, in a New York Times/CBS News poll released in March, twice the gender gap of the 2012 presidential election, when President Obama defeated Mr. Romney.

Mrs. Clinton’s campaign, which cannot directly coordinate with the super PAC, has tried to raise money by showing Mr. Trump’s comments assailing the former secretary of state for playing the “woman’s card.”

Mrs. Clinton, though, has tried to avoid directly provoking Mr. Trump, relying instead on outside groups like the super PAC to carry out direct attacks. The campaign’s online videos against Mr. Trump have focused mostly on his policy positions and on criticism by his rivals in the Republican primaries.

On Tuesday, Mr. Trump said the “Speak” ad had misrepresented one of his statements. “The pathetic new hit ad against me misrepresents the final line. ‘You can tell them to go BLANK themselves’ — was about China, NOT WOMEN!” he wrote on Twitter.

That drew a rebuke from the super PAC.

“Sorry Donald, but the ad isn’t only about your overt sexism, it’s about your divisiveness and character being unsuitable for the office of the presidency,” Justin Barasky, a spokesman for the group, said in an email on Tuesday morning.