Suppose $\preceq$ was an order on $(\Bbb R^*,\cdot)$. Now let's pose the question - which is larger with respect to $\preceq$, $-1$ or $1$? If $-1\prec1$, then by multiplying both sides by $-1$ we should have $(-1)\cdot(-1)\prec1\cdot(-1)$, so $1\prec -1$, which is impossible. Similarly we cannot have $1\prec -1$, so this group cannot be totally ordered.
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I believe it's because multiplication by a negative is order reversing. The operation is not strictly order preserving. But if you just restrict to the positive real numbers $\Bbb R^{+}$ then it is an ordered group under multiplication.
Suppose $\preceq$ was an order on $(\Bbb R^*,\cdot)$. Now let's pose the question - which is larger with respect to $\preceq$, $-1$ or $1$? If $-1\prec1$, then by multiplying both sides by $-1$ we should have $(-1)\cdot(-1)\prec1\cdot(-1)$, so $1\prec -1$, which is impossible. Similarly we cannot have $1\prec -1$, so this group cannot be totally ordered.