Dihydrocarvone과 Formaldehyde에 의한 향료 합성

Abstract

(+)-Dihydrocarvone(p-mentha-8-ene-2-one)을 alkali 촉매하에서 formaldehyde로 hydroxymethylation하여, 1β-hydroxymethy1-p-mentha-8-ene-2-one(Ⅰ)과 lα-hydroxymethy1-p-mentha-8-ene-2-one(Ⅱ)을 합성하였다. 이 반응은 aldol condensation으로 ketone의 α-위치(C-1)에 regiospecific하게 진행하였다. Ⅰ과 Ⅱ를 LiAlH_(4)로 환원하여 1β-hydroxymethy1-p-mentha-8-ene-2β-ol(Ⅲ)과 1α -hydroxymethy1-p-mentha-8-ene-2β-ol(Ⅳ)을 얻었다. 그리고 Ⅰ과 Ⅱ를 CrO_(3)로 Corey oxdation법과 Jones oxidation법에 의해 각각 산화하여 1β-formy1-p-mentha-8-ene-2-one(Ⅴ), 1α-formy1-p-mentha-8-ene-2-one(Ⅵ), 1β-carboxy-p-mentha-8-ene-2-one(Ⅶ), 1α-carboxy-p-mentha-8-ene-2-one(Ⅷ)을 합성하였다. 또한 Ⅰ과 Ⅱ를 tosylester화 하여 LiALH_(4)로 환원하고, 다시 CrO_(3)로 산화하여 1-methy1-p-mentha-8-ene-2-one(Ⅸ)를 얻었다. 새로이 합성된 물질 Ⅰ-Ⅸ 중 Ⅶ,Ⅷ,Ⅸ 등은 carvone, camphor 계열의 항을 지닌다.;The synthetic product of l-hydroxymethyl-p-mentha-8-ene-2-one was afforded by the reaction of dihydrocarvone with formaldehyde, This reaction involves the aldol condensation. The preferential position of formaldehyde is methyl substituted α-carbon atom where the 1.2-enolate of p-mentha-8-ene-2-one is regiospecifically formed. The hydroxymethylation of dihydrocarvone also proved to occur regiospecifically in the position of α-methyl substituted ketone(C-1). When I-hydroxymethyl-p-mentha-8-ene-2-one reacted with LiAlH_(4). l-hydroxymethyl-p-mentha-8-ene-2β-o1 was obtained. l-Hydroxymethyl-p-mentha-8-ene-2-one also reacted with chromic acid to give 1-formyl-p-mentha-8-ene-2-one and l-carboxy-p-mentha-8-ene-2-one. When the hydroxymethyl group of l-hydroxymethyl-p-mentha-8-ene-2-one was reduced to methyl group, l-methyl-p-mentha-8-ene-2-one was obtained. Some of these new compounds have certain odor.