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I would say that it was in Genesis 3:15, when God cursed the serpent (which, acting as an agent possessed by Satan, had deceived Eve, ultimately resulting in both Eve and Adam disobeying God and falling into sin by eating the fruit of the tree of the knowledge of good and evil in the Garden of Eden, from which God had commanded them not to eat). At that time, God said that one of Eve's descendants (or her "seed" in Biblical language) would mortally bruise (or crush) the head of the serpent, thus inflicting an ultimately fatal wound on Satan as the serpent's actuator. Although the fulfillment of this prophecy did not occur until thousands of years later, it was realized by Christ's sinless life, redeeming death (to which God referred when He spoke of the serpent bruising the heel of the woman's seed) and His subsequent resurrection.
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