Selective hydroxymethylation of furfuryl alcohol with aqueous formaldehyde in the presence of dealuminated mordenites

doi:10.1016/S0926-860X(97)00349-9

Applied Catalysis A: General

Volume 168, Issue 2, 27 March 1998, Pages 235-241

https://doi.org/10.1016/S0926-860X(97)00349-9 Get rights and content

Abstract

Hydroxymethylation of furfuryl alcohol with aqueous formaldehyde, yielding selectively 2,5-bis(hydroxymethyl)furan, has been carried out in the presence of various dealuminated H-form mordenites. The best results expressed in terms of both selectivity (≥95%) and conversion (≥70%) are obtained over H-MOR 100 catalyst (0.25 g) using a furfuryl alcohol/formaldehyde molar ratio of 0.009 after short reaction times (≤30 min) and at low temperatures (313–327 K).

Introduction

Reactions of furan and its derivatives with formaldehyde have received little attention because Friedel-Crafts alkylation of furans usually leads to complicated reaction mixtures due to the high reactivity of these heterocycles [1]. As a matter of fact, oligomers, resinification of furan compounds and other decomposition products are obtained upon heating and in the presence of an acidic catalyst [2].

One of the valuable products in the furan series is 2,5-bis(hydroxymethyl)furan (BHMF), useful as intermediate in the synthesis of drugs [3], crown ethers [4], and polymers [5]. It is generally produced either through reduction of 5-hydroxymethylfurfural, or through condensation of furfuryl alcohol with formaldehyde.

In spite of high yields (90%–96%), 5-hydroxymethylfurfural reduction processes with sodium amalgam [6]or hydrogen over Cu–Cr catalyst [7]are limited because of the not readily available starting material (HMF).

Single step BHMF synthesis by hydroxymethylation of the easily available furfuryl alcohol by formaldehyde requires mild acidic conditions. Thus, 2,5-bis(hydroxymethyl)furan can be obtained in yields of 75%–80% with acetic acid as solvent and catalyst [8]. By contrast, furfuryl alcohol hydroxymethylation with aqueous formaldehyde, in the presence of weakly acidic ion-exchange resins in their H⁺ form [9], has not led to such high yields (only 25%–30% of isolated pure product after 120 h reaction time). Moreover, condensation and polymerisation products are generally obtained when strong acids are used.

Our interest in the use of zeolites in liquid phase reactions led us to substitute zeolites for cation-exchange resins which do not have high reactivity and selectivity in furfuryl alcohol hydroxymethylation.

High-silica zeolites, such as dealuminated mordenite and ZSM-5 are known to be hydrophobic [10]. These zeolites are then expected to have a high activity as solid acid catalysts in aqueous solution. Large pores zeolites, such as mordenites [11], have been chosen because the reaction takes place inside the pores, whereas a liquid phase reaction generally occurs on the external surface of medium-pores ZSM5 12, 13.

Section snippets

Experimental

Furfuryl alcohol was distilled before use; formalin (37 wt % aqueous formaldehyde stabilised with 10%–15% methyl alcohol) was from Aldrich and used as such. Catalysts, supplied by Zeocat, were dealuminated mordenites in their protonic form. The typical properties of these catalysts are shown in Table 1.

The reactions were carried out in a glass reactor working in the batch mode. Except otherwise mentioned, the general procedure was as follows: 6 ml of formalin were added to the zeolite (250 mg). The

Reaction scheme

The overall reaction scheme (Scheme. 1) can be depicted as:

Reaction 1: Hydroxymethylation of furfuryl alcohol, under acidic conditions as a Friedel-Crafts type reaction leading to BHMF formation.
Reaction 2: Condensation of BHMF on FA to produce bis(2-hydroxymethyl-5-furyl)methane.
Reaction 3: Resinification of furfuryl alcohol. The acid-catalysed resinification mechanism involves first the condensation (alkylation) of a hydroxymethyl group at the C-5 of the furan nucleus to give predominantly

Conclusion

To our knowledge, selectivities as high as 95%–98% towards BHMF have not been reported for heterogeneous hydroxymethylation of furfuryl alcohol.

Under mild conditions (313–327 K), H-MOR 100 exhibits high activity for furfuryl alcohol hydroxymethylation as evidenced by the high product selectivity and the low by-product formation. This selectivity depends on the temperature and/or the furfuryl alcohol/formaldehyde molar ratio. For example, if this ratio is 0.009, a high BHMF selectivity (≥95%) is

Acknowledgements

Thanks are due to Agrichimie S. A. (la Martinique) for financial support and the permission to publish this work. Furthermore, the authors are grateful to Zeocat for providing zeolite samples.

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Selective hydroxymethylation of furfuryl alcohol with aqueous formaldehyde in the presence of dealuminated mordenites

Abstract

Introduction

Section snippets

Experimental

Reaction scheme

Conclusion

Acknowledgements

Appl. Catal.

J. Catal.

Mater. Chem. Phys.

Stud. Surf. Sci. Catal.

J. Am. Chem. Soc.