Two alternative routes for 1,2-cyclohexanediol synthesis by means of green processes: Cyclohexene dihydroxylation and catechol hydrogenation

• The dihydroxylation of cyclohexene gives 97.4% yield to 1,2-cyclohexanediol.
• The catalyst is made of WO42−/PO43−, in a biphasic system.
• Important parameters in cyclohexene dihydroxylation are T and H2O2 concentration.
• Selective hydrogenation of catechol gives 90% yield to 1,2-cyclohexanediol.
• The catalyst for hydrogenation is made of Ru(OH)3/Al2O3.

In this paper we compare two different reactions, aimed at the synthesis of 1,2-cyclohexanediol. Specifically: (a) the direct epoxidation and hydrolysis (dihydroxylation) of cyclohexene to trans-1,2-cyclohexanediol, with an aqueous solution of hydrogen peroxide, and (b) the hydrogenation of catechol to a mixture of cis and trans-1,2-cyclohexanediol, in an attempt to establish green protocols for the synthesis of diols. Both reactions, the dihydroxylation of cyclohexene and the hydrogenation of catechol, were carried out without organic solvents. In the former case, an unprecedented 97.4% yield to the glycol was obtained, by selecting proper reaction conditions and using a tungstic acid/phosphoric acid catalyst, in a biphasic system with a phase-transfer agent. In the second approach, a heterogeneous alumina-supported Ru(OH)x catalyst was used, and a 90% yield to the glycol was obtained. A comparison of the two processes allowed to show the lower environmental impact of the catechol hydrogenation route.

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