Some of the 1-byte opcodes are specific subsets of instructions (e.g., 04 is ADD AL, Ib). Keeping in mind that many single-byte opcodes don't actually exist in 64-bit code (e.g., PUSH DS or DAS), the ones that do exist that aren't used:
ins, outs, lods, in, stc, cli, wait, pushf, popf, lahf