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From When. The Tana is referring to a Possuk as it says in the Possuk, "When you lie down and when you get up." From there we learn that it is an obligation on each man to read Shema in the evening and in the morning. And the Mishna now asks when is the time? and from the Possuk that says when you lie down at the beginning, we start with the evening Shema.

Introduction Tractate Berakhot begins by discussing what time the Shema (only two paragraphs were recited at night, Deuteronomy 6:4-9 and 11:13-21) is recited in the evening. It probably begins by discussing the evening Shema because in rabbinic thought the day begins at night. This is also the order reflected in Deuteronomy 6:7 and 11:19, “Recite them…when you lie down and when you get up.” In our mishnah the sages debate what the halakhic meaning of the words “when you lie down” really are.

עד סוף האשמורה הראשונה – The first third of the night (is the end of the first “watch”), as the night is divided into three watches, and from then onwards is no longer called the time [for the] Recitation of the Shema (Deuteronomy 6:4-9; 11:13-21; Numbers 15:37-41) when lying down, and we do not refer to it as “when you lie down” (Deuteronomy 6:7), and prior to the stars coming out (literally, “going out”), it is also considered daytime and not the time of lying down. And those who recite Evening Shema early while it is still day, rely upon that [opinion] of Rabbi Yehuda who said further on in Chapter “Tefillat HaShahar”/The Morning Prayer/Amidah (Chapter 4 of Berakhot, Mishnah 1), that the Afternoon prayer is recited until “Plag HaMinhah”/the middle of the afternoon (the half-way point between the time when the Tamid/Daily Sacrifice was offered – 3:30 pm and 6:00 pm when the time of sunset arrives at the Vernal and Autumnal Equinoxes), which is an hour and a quarter prior to the night time. And we establish (literally, “hold”), that he followed [the opinion of] Rabbi Yehudah, and immediately when the time for Minhah ends, the time for the Evening Recitation of the Shema begins.