Synthesis of Natural Compounds with Alkyl‐methoxy‐1,4‐benzoquinone StructureThe 1,4‐benzoquinones1–7occurring in various plants and having interesting biological properties have been synthesized from the tetrahydropyranyl ethers17and21. Reaction withn‐butyllithium gave selectively theortho‐lithiated compounds. These could be alkylated with the haloalkenes13–16and haloalkanes to give the substituted phenols18–20and22–25in high yield after methanolysis. Alkylations of the methoxyisopropylether8of 10‐undecyn‐1‐ol with bromobutane and bromohexane gave9and10. These alkynols could be selectively hydrogenated with Lindlar‐Palladium catalyst to give the (Z)‐alkenols11and12which could be converted into the bromoalkenes13, 14and the iodoalkenes15, 16. Oxidation of the phenols18–20and22–25with molecular oxygen in the presence of salcomine as catalyst produced the substituted 1,4‐benzoquinones1–3and26–29in high yield. Selective hydrolysis with perchloric acid con