酢酸イソプレギルおよび酢酸ネオイソプレギルの二酸化セレン酸化

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概要

• 論文の詳細を見る

• Isopulegyl acetate [1] and neo-isopulegyl acetate [2] were oxidized with selenium dioxide in aqueous ethanol under reflux. The oxidation of (-) - [1] gave (-) - (1R : 3R : 4S) -8 (10) -p-menthene-3-acetoxy-9-al [1a] and -9-ol [1b]. The oxidation of (+) - [2] gave (+) - (1R : 3S : 4S) -8 (10) -p-menthene-3-acetoxy-9-al [2a], -9-ol [2b], (-) - (1R : 3S : 4S) -8-p-menthene-3-acetoxy-4-ol [2c], (+) - (1R : 3S : 4R) -8-p-menthene-3-acetoxy-4-ol [2d] and (+) - (1R : 3S : 4R) -8 (10) -p-menthene-3-acetoxy-4, 9-diol [2e]. The mechanism of allylic oxidation of olefins with selenium dioxide was visualized in two stages, the first involving the formation of the allylic selenite ester and the second the solvolysis of this ester. In the case of [2], the allylic selenite ester [A] and [B] were produced and then the solvolysis of these esters gave -9-ol [2a] and -4-ols ([2c], [2d]) respectively. In the case of [1] the formation of the allylic selenite ester [C] is required for the production of -4-ol. Since the ester [C] introduces an interaction between acetoxy group and isopropylidene group by eclipsing, the formation of [C] would be unfavorable. In agreement with this, GLC analysis failed to show the presence of any -4-ols. In the solvolysis step of [A], the trans-attack of the water molecule to acetoxy group would be preferable to the alternative cis-attack, since the cis-attack produces a skew-like interaction between acetoxy group and hydroxy group. Indeed the yield of [2d] produced by the trans-attack was twice the yield of [2c] produced by the cis-attack.

• 日本油化学会の論文

著者

• 作田 芳次

  高知女子大学化学研究室

• 田原 敏恵

  高知女子大学化学研究室

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