I found this generalization of the "$3 \pmod{4}$" version while teaching number theory a few years ago.
Let $G$ be a proper subgroup of $(\mathbb{Z}/n)^\times$. Then there are infinitely many primes $p$ such that $[p]\in (\mathbb{Z}/n)^\times$ and $[p]\not\in G$.
Proof: Suppose as usual that there are finitely many, $p_1, p_2, \ldots, p_r$, and find a number $g$ such that $(p_i,g) = 1$ for all $i$ and $[g]\not\in G$. Then the number $N = np_1 p_2 \cdots p_r + g$ has a prime factorization $N = q_1q_2 \cdots q_s$ satisfying
- $q_i \neq p_j$ for all $i$ and $j$ and
- since $[N]=[g]\not\in G$, $[q_i]\not\in G$ for at least on $i$.
EDIT 8-29-20
Here is a detailed proof. There's a bit of fun messing around to find the right number $N$.
Theorem. Let $m\in \mathbb{N}$ and let $G\subseteq (\mathbb{Z}/m)^\times$ be a proper subgroup. Then %for each %$\alpha\in (\mathbb{Z}/m)^\times - G$, there are infinitely many primes $p$ such that $[p] \in (\mathbb{Z}/m)^\times - G$.
Proof.
Assume to the contrary that there are only finitely
such primes,
$$
\mathcal{P}
=
\{
\mbox{all primes $p$ such that
$[p] \in (\mathbb{Z}/m)^\times -G$}
\}
=
\{ p_1, p_2, \ldots, p_r\}.
$$
Since each
$[p_i]\in (\mathbb{Z}/m)^\times$
we have $(p_i,m) = 1$ for $i= 1, 2, \ldots, r$.
Since $G$ is a proper subgroup of $(\mathbb{Z}/m)^\times$,
we can find an integer $a$ such that
$[a]\in (\mathbb{Z}/m)^\times - G$;
again $(a, m) = 1$.
Now we inductively define a sequence of integers
$N_k$ for $k = 0, 1, 2, \ldots, r$ with the properties
- $N_k \equiv a$ mod $m$
- $(p_i, N_k) = 1$ for $i=1, 2, \ldots, k$.
The construction begins with
$
N_0 = mp_1p_2 \cdots p_r + a .
$
Once we have $N_k$, we define
$$
N_{k+1} =
\left\{
\begin{array}{ll}
N_k & \mbox{if $(p_{k+1}, N_k) = 1$}
\\
\\
N_k + m p_1p_2\cdots p_k & \mbox{if $p_{k+1} | N_k$.}
\end{array}
\right.
$$
Obviously
$N_{k+1} \equiv N_k\equiv a$ mod $m$,
and $N_{k+1} \equiv N_k$ mod $p_i$ for each
$i = 1, 2, \ldots, k$, so that
$$
(N_{k+1}, p_i) = (N_k , p_i) = 1
$$
for $i = 1, 2, \ldots, k$. Furthermore,
if $p_{k+1}| N_k$, then $p_{k+1}$ cannot
divide $N_{k+1}$, lest $p_{k+1}$ divide
$m p_1p_2\cdots p_k$, which is impossible. Therefore
the construction continues, and ultimately
obtain the integer $N_r$.
Now consider its prime factorization
$
N_r = q_1q_2 \cdots q_s
$.
We can say from what we have done that
- $q_j \neq p_i$ for any $i$ and $j$, so
$[q_j] \in G$ for all $j =1, 2, \ldots, s$, and so
- $[N_r] = [q_1]\cdot [q_2] \cdots [q_s] \in G$, but
- $[N_r] = [ a] \not\in G$.
This contradiction of the last two lines
shows that our assumption that
there are only finitely many such primes $p$
such that $[p]\in (\mathbb{Z}/m)^\times - G$
must be wrong,
and this completes the proof.