substrate dependence in aqueous diels-alder reactions of cyclohexadiene derivatives with 1,4-benzoquinone底物的依赖与1水diels-alder反应环己二烯衍生品,4-benzoquinone.pdfVIP

Molecules 2005, 10, 244–250 molecules ISSN 1420-3049 Substrate Dependence in Aqueous Diels-Alder Reactions of Cyclohexadiene Derivatives with 1,4-Benzoquinone Takeshi Sunakawa and Chiaki Kuroda* Department of Chemistry, Rikkyo University, Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan. Tel.: (+81)339852396, Fax: (+81)359923434 * Author to whom correspondence should be addressed; e-mail kuroda@rikkyo.ac.jp Received: 10 May 2004; in revised form: 25 November 2004 / Accepted: 25 November 2004 / Published: 31 January 2005 Abstract: A reactivity difference based on the position of substituents on cyclohexa-1,3- diene was observed for the title reaction. The effect of water as solvent was more distinct for 1-methyl-4-isopropylcyclohexa-1,3-diene than for 2-methyl-5-isopropylcyclohexa- 1,3-diene or non-substituted cyclohexa-1,3-diene. The effect of NaCl (salting-out) and guanidium chloride (salting-in) was also large for 1-methyl-4-isopropylcyclohexa-1,3- diene. Keywords: Diels-Alder reaction, aqueous, cyclohexadiene, substrate dependence Introduction Recently, the development of organic reactions in aqueous media has been remarkable [1], especially in light of the interest in “green chemistry”. Among the various reactions, the Diels-Alder reaction is well documented [2,3]. The effect of micelles [4] or Lewis acids [5], including Lewis acid-surfactant combinations [6] have also been studied for the aqueous Diels-Alder reaction. In contrast to the reaction in organic solvents, the water-based r