The answer to the title question is no and the answer to the body question is yes.
First, Stickelberger's theorem asserts that the discriminant $\Delta_K$ of a number field $K$ is congruent to $0, 1 \bmod 4$. So that already rules out half of the possibilities.
Second, Minkowski's bound implies that if $K$ has degree $n$ then
$$\sqrt{|\Delta_K|} \ge \left( \frac{\pi}{4} \right)^{n/2} \frac{n^n}{n!}.$$
The RHS is always strictly bigger than $1$, so the discriminant can also never be equal to $1$; that is, $\mathbb{Q}$ has no unramified extensions. Moreover it follows that number fields of a given discriminant cannot have arbitrarily high degree, and in fact there are only finitely many number fields of a given discriminant, so for particular small discriminants one can rule them out via casework.
To start, let's record the value of the Minkowski bound for some small values of $n$.
- For $n = 2$ it is about $1.57$, so a number field of degree at least $2$ has discriminant of absolute value at least $3$.
- For $n = 3$ it is about $3.13$, so a number field of degree at least $3$ has discriminant of absolute value at least $10$.
- For $n = 4$ it is about $6.58$, so a number field of degree at least $4$ has discriminant of absolute value at least $44$.
Let's also recall that for a squarefree integer $d$ the discriminant of $\mathbb{Q}(\sqrt{d})$ is $d$ if $d \equiv 1 \bmod 4$ and $4d$ otherwise. Now let's go through the smallest few discriminants in order, skipping the ones that are impossible by Stickelberger to see what Minkowski has to say about them.
- $1$: impossible by Minkowski.
- $-3$: realized uniquely by $\mathbb{Q}(\sqrt{-3})$.
- $4$: impossible by Minkowski (can only be realized by a quadratic field and isn't).
- $-4$: realized uniquely by $\mathbb{Q}(i)$.
- $5$: realized uniquely by $\mathbb{Q}(\sqrt{5})$.
- $-7$: realized uniquely by $\mathbb{Q}(\sqrt{-7})$.
- $8$: realized uniquely by $\mathbb{Q}(\sqrt{2})$.
- $-8$: realized uniquely by $\mathbb{Q}(\sqrt{-2})$.
- $9$: impossible by Minkowski (can only be realized by a quadratic field and isn't).
- $-11$: realized by $\mathbb{Q}(\sqrt{-11})$.
- $12$: realized by $\mathbb{Q}(\sqrt{3})$.
$-12$ is the first discriminant whose status I can't determine from just Stickelberger and Minkowski. If it occurs as a discriminant it must be the discriminant of a cubic field. I think it's known that in fact the smallest possible discriminant (in absolute value) of a cubic field is $-23$, realized by $\mathbb{Q}(x)/(x^3 - x - 1)$, but I don't know how to prove this.
In any case, here's a discriminant I can rule out using an additional technique: $25$ is congruent to $1 \bmod 4$ and, by the Minkowski bound, could only be the discriminant of a cubic field. However, I claim it isn't the discriminant of a cubic field, and so can't be a discriminant at all. The reason is that it's a square, which means that the corresponding cubic field is Galois with Galois group $A_3 \cong C_3$. By the Kronecker-Weber theorem it must therefore be a subfield of the cyclotomic integers $\mathbb{Q}(\zeta_n)$, and it's known that we should in fact be able to take $n = 5$. However, $\mathbb{Q}(\zeta_5)$ has no cubic subfields since it has degree $4$.