I'll assume that you're assaying dl-alpha tocopherol, not dl-alpha tocopheryl acetate. We've done both by GC, straightforward, high temperaturs are required. Now dl-alpha tocopherol is not all that stable, so personally I would not use KOH or saponify first. The dl-alpha tocopherol is more soluble in solvents such as N,N-dimethylformamide (DMF) and alcohols than is the sunflower oil. You could use hexane or heptane as solvent, but I think I'd use DMF or alcohol, heat and stir, cool it (most of the sunflower oil should separate and float on the top), and inject the solvent portion into the GC. If I understand your wording correctly, hexadecyl hexadecanoate would probably be an internal standard, and is the ester of hexadecanoic acid and hexadecanol (cetyl palmitate).