2-(2-メチル-1-プロペニル)-4-メチルテトラヒドロ-2H-ピラン

化学的特性Rose Oxide occurs in small quantities, mainly as the levorotatory cis form, in essential oils (e.g., Bulgarian rose oil and geranium oil). Commercial synthetic products are either optically active or inactive mixtures of the cis- and trans-isomers. Their sensory properties depend on the starting material and the method of synthesis.They are colorless liquids with a strong odor reminiscent of geranium and rose oil.

解説ローズオキシド．ローズ油中の微量成分．クトロンアルデヒドとビニルエチルエーテルのジエン付加物より，α-ブロモ-γ-メチルテトラヒドロピランを得て，そのグリニャール反応により，シス，トランス混合物を得る．無色の液体．沸点182 ℃．d25250.870．n20D1.4566．質のよい花様の香りを有する．バラ系調合香料，せっけんの香料に用いられる．LD50 ＞ 5000 mg/kg(ウサギ，経皮)．

天然物の起源Reported found in the oils of rose (Bulgarian) and geranium (Réunion); both the cis- and the trans-form have been reportedly isolated from geranium oil. Unidentified isomers reported found in black currant berries, passion fruit, some types of Thymus and white wine.

製造方法Rose oxide is usually prepared from citronellol, which can be converted into a mixture of two allyl hydroperoxides by photosensitized oxidationwith singlet oxygen. Reduction of the hydroperoxideswith sodium sulfite yields the corresponding diols . Treatmentwith dilute sulfuric acid results in allylic rearrangement and spontaneous cyclization of one of the isomers; amixture of diastereoisomeric rose oxides is thus formed. The unreacted diol isomer is separated by distillation. ()- Citronellol as the starting material yields an approximately 7 : 3 mixture of ()-cisand ()-trans-rose oxide. Higher proportions of the cis-isomer may be obtained by dehydration with a stronger acid.Other methods for the production of rose oxide starting from citronellol consist of halogenation–dehalogenation reactions of citronellol.An alternative technical process does not use citronellol but starts from prenal [107-86-8] and 3-methyl-3-buten-1-ol [763-32-6]. Under acidic conditions, the reaction affords a mixture of isomers of dehydro rose oxide (C10H16O6; [1786- 08-9], [92356-05-3], [60857-05-8]). Subsequent hydrogenation using a ruthenium/alumina catalyst leads to rose oxide.The proportion of cis-isomer can be increased by isomerization under acidic conditions.