Abstract
A synthesis is proposed of 4,8-dimethyldecanal (VIII) — a pheromone of the flour beetlesTribolium confusum andT. castaneum. By heating 71.2 g of 4-methyltetrahydropyran (I), 83.2 g of AcBr and 1.57 g of ZnCl2 (45°C), then 120°C, 2 h), 1-acetoxy-5-bromo-3-methylpentane (II) was obtained. The hydrolysis of 19.8 g of (II) (MeOH-H2O, TsOH, 20°C, 15 h) gave 5-bromo-3-methylpentan-1-ol (III). From 18.1 g of (III) and 38.9 ml of 2,3-dihydropyran (Et2O, TsOH, 20°C, 20 h) was obtained the 2-THPL ester of (III), (IV), which was converted into 3-methyloct-7-en-1-ol (V) by the treatment of the corresponding Grignard reagent with allyl bromide (THF, CuI-bi-2-pyridyl, 2°C, 4 h, Ar). The interaction of 1.42 g of (V) with Et3Al (hexane, 20°C, Cp2ZrCl2, Ar) gave 3,7-dimethylnonan-1-ol (VI), boiling which with 48% HBr in the presence of concentrated H2SO4 gave 1-bromo-3,7-dimethylnonane (VII) which was then converted into the desired (VIII) by the reaction of the corresponding Grignard reagent with DMFA (0–2°C, 1 h; 20°C, 2 h; Ar). The characteristics of the compounds — yield (%), nD (°C): (I), 79, 1.4340 (22); (III) 89, 1.4660 (23); (IV), 82, 1.4739 (23); (V), 85, —; (VI), 90, 1.4483 (20); (VII), 88, 1.4409 (22); (VIII), 88, 1.4589 (22). Details of the IR and PMR spectra of compounds (II)–(VII) are given.
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Institute of Chemistry, Bashkir Scientific Center, Urals Branch, USSR Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 272–276, March–April, 1989.
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Odinokov, V.N., Izhmuratov, G.Y., Kharisov, R.Y. et al. Pheromones of insects and their analogs. XX. Methyl-branched pheromones based on 4-methyltetrahydropyran.. Chem Nat Compd 25, 236–239 (1989). https://doi.org/10.1007/BF00598420
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DOI: https://doi.org/10.1007/BF00598420