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This event has not happened yet. Hillary Clinton made a serious bid for the nomination but did not succeed. Mrs. Edith Wilson was said by some to have made herself the acting president after President Wilson had a stroke in September, 1919. She screened the president's messages and decided what was important enough to bring to the President.
John F. Kennedy's father, Joe Kennedy, was once the ambassador for the USA in the UK.
Hobos
Martha Washington was the wife of US President George Washington long before he became president. She was an aristocrat and became the first of the group called "First Ladies", meaning the wives of US Presidents.
14 so far.You can read more at:What_vice_presidents_became_president
(1969-1979)she was ambassador to Czechoslovakia
Eklil Ahmad Hakimi is the Ambassador to the US for Afghanistan.
Mohamed Tawfik is the Ambassador to the US for Egypt.
Tatoul Markarian is the Ambassador to the US for Armenia.
Josko Paro is the Ambassador to the US for Croatia.
Mrs. Herbert Hoover was named Lou.
Peter Taksoe-Jensen is the Ambassador to the US for Denmark.