Encouraged by the proof in the answer by Fedor Petrov, I started random search and found such subsets for each $n\leqslant200$ starting from $n=7$, which in addition satisfy the condition imposed by Fedor: for all $i\ne j$, either $i\in B(j)$ or $j\in B(i)$. Here is one for $n=7$:
$$
\begin{aligned}
B(1)&=\{2,3,5\},\\
B(2)&=\{3,4,6\},\\
B(3)&=\{4,5,7\},\\
B(4)&=\{5,6,1\},\\
B(5)&=\{6,7,2\},\\
B(6)&=\{7,1,3\},\\
B(7)&=\{1,2,4\}.
\end{aligned}
$$
As noticed in the comment by Gerhard "Nothing Escapes Him" Paseman, this one can be realized by a bijection between points and lines of the Fano plane.
Later
Here is, in fact, a (one of many) simple inductive construction of a tournament $B_n$ on vertices $\{1,...,n\}$ with needed properties for each $n\geqslant7$.
For $n=7$ just take $B_7(k)=B(k)$, $k=1,...,7$, with $B$ the one above.
Then for $n>7$ let $B_n(n)=B_7(7)=\{1,2,4\}$ for $n$ odd and $B_n(n)=B_7^{-1}(7)=\{3,5,6\}$ for $n$ even, and
$$
B_n(k)=
\begin{cases}
B_{n-1}(k)\cup\{n\},&k\notin B_n(n),\\
B_{n-1}(k),&k\in B_n(n)
\end{cases}
$$
for $k=1,...,n-1$. That's it.
Still later
The proof seems to be not entirely trivial, so I decided to supply at least a sketch of it.
Let us denote for simplicity $i\in B(j)$ by $j\to i$. Note that for tournaments (i. e. when exactly one of $i\to j$ or $j\to i$ holds iff $i\ne j$), the requirements are equivalent to the existence, for all $i\to j$, of a $k$ with $i\to k\to j$.
Now by induction, if $B_{n-1}$ satisfies this, we have to check the above for $n\to i$ and for $i\to n$.
Now if $n\to i$ holds (i. e. $i\in B_n(n)$), then, noting that each $B_n(n)$ is in fact a 3-cycle (either $1\to2\to4\to1$ or $3\to5\to6\to3$), there always is a $j\in B_n(n)$ (i. e. $n\to j$) with $j\to i$.
And if $i\to n$ holds then $i\notin B_n(n)$, and, again by induction (see below), there is a $j\notin B_n(n)$ (hence $j\to n$) with $i\to j$.
To complete the induction, it remains to show that ($n\notin B_{n+1}(n+1)$ and) there is a $j\notin B_{n+1}(n+1)$ with $n\to j$. This is clear since $B_n(n)$ and $B_{n+1}(n+1)$ do not intersect, so we can take any $j\in B_n(n)$.