Let us put an additional blue ball in position $0$, to the left of the $n$ balls.
The condition on the permutations of the $n$ balls is then that the marked red ball be preceded by an odd number (say $2r-1$) of red balls, which in turn must be preceded by a blue ball. Let us refer to such permutations as good.
Let $p_{n,k}$ denote the number of good permutations of the $k$ red balls and $n-k$ blue ones.
Let $j$ be the position of the marked red ball in a good permutation. Then $j\ge2r$.
If $j=2r$, then $j$ is even and the only blue ball to the left of the marked red ball is the additional blue ball in position $0$. So, for any given even $j\in[n]:=\{1,\dots,n\}$, the number of good permutations with $2r=j$ is
\begin{equation*}
\Big(\prod_{i=0}^{j-2}(k-1-i)\Big)(n-j)!=\frac{(k-1)!(n-j)!}{(k-j)!}.
\end{equation*}
(If $j>k$, then the latter fraction is understood as $0$.)
Similarly counted are the good permutations with $j>2r$, where we must use one of the $n-k$ blue balls to place it immediately to the left of the $2r-1$ red balls preceding the marked red ball.
Thus,
\begin{equation*}
\begin{aligned}
p_{n,k}&=\sum_{j\in[n]}\Big(
1(j\text{ is even})\frac{(k-1)!(n-j)!}{(k-j)!} \\
&+\sum_{1\le r<j/2}(n-k)\frac{(k-1)!(n-2r-1)!}{(k-2r)!}
\Big) \\
&=(k-1)!\sum_{j\in[k]}
1(j\text{ is even})\frac{(n-j)!}{(k-j)!} \\
&+(k-1)!(n-k)
\sum _{r=1}^{\lfloor k/2\rfloor } \frac{(n-2 r)!}{(k-2 r)!} \\
&=(k-1)!(n-k+1)
\sum_{r=1}^{\lfloor k/2\rfloor } \frac{(n-2 r)!}{(k-2 r)!}.
\end{aligned}
\end{equation*}
This very simple expression is easy to analyze. Indeed, consider what is, according to the OP's comment, the case of interest: $n=2k-1$. Then
\begin{equation*}
p_{n,k}=q_k:=p_{2k-1,k}=k!\sum_{r=1}^{\lfloor k/2\rfloor } \frac{(2k-1-2 r)!}{(k-2 r)!}.
\end{equation*}
The OP wanted to show that
\begin{equation*}
P_k:=\frac{q_k}{(2k-1)!}
\end{equation*}
is $\le1/3$ and $P_k\to1/3$ as $k\to\infty$.
To prove this, write
\begin{equation*}
P_k=\sum_{r=1}^\infty a_{k,r}, \tag{1}\label{1}
\end{equation*}
where
\begin{equation*}
a_{k,r}:=\frac{k!}{(2k-1)!} \frac{(2k-1-2 r)!}{(k-2 r)!};
\end{equation*}
the latter fraction is understood as $0$ if $2r>k$. We can also write
\begin{equation*}
a_{k,r}=\prod_{i=0}^{2r-1}\frac{k-i}{2k-1-i}
=\frac{k}{2k-1}\prod_{i=1}^{2r-1}\frac{k-i}{2k-1-i}
\le \frac{k}{2k-1}\frac1{2^{2r-1}}.
\end{equation*}
It also follows that $a_{k,r}\to\frac1{2^{2r}}$ as $k\to\infty$, for each natural $r$. So, by \eqref{1} and dominated convergence,
\begin{equation*}
P_k\to\sum_{r=1}^\infty \frac1{2^{2r}}=\frac13, \tag{2}\label{2}
\end{equation*}
as was desired.
Next, it is easy to see that, for each natural $r\ge2$, $a_{k,r}$ is increasing in natural $k\ge2r$. A little complication here is that $a_{k,1}$ is decreasing in $k$. However, it is rather easy to see that $\sum_{r=1}^3 a_{k,r}$ is increasing in natural $k\ge5$. So, by \eqref{1}, $P_k$ is increasing in natural $k\ge5$.
So, by \eqref{2}, $P_k<1/3$ for $k\ge5$. It also easy to see that $P_k<1/3$ for $k\in\{1,3,4\}$ and $P_2=1/3$.
Thus, $P_2=1/3$ and $P_k<1/3$ for $k\in\{1,3,4,5,6,\dots\}$, as was also desired.