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By adjusting the acidity of the solvent, an alternative mechanism is discovered in which the reaction selectivity stops to the hydroxymethylation step, in contrast to previously reported acid\u2010catalyzed pathways leading to the formation of the bisfuranic dimer as a major product. One of the keys of this study relies on the reversible derivation of the \u2013CHO group of furfural with <jats:italic>N,N<\/jats:italic>\u2010Dimethylhydrazine which plays a dual role: (1) it restores the nucleophilicity of the furan ring and (2) it reacts with HCHO to form in situ an electrophilic zwiterrionic species stabilized through hydrogen transfer. By means of experimental and theoretical investigations, this reaction is optimized and it is discovered that guaiacol can be used as a bio\u2010based and safe solvent. Under optimized conditions, the hydroxymethylation of the furan ring of furfural occurs with more than 95% selectivity, at only 50\u2009\u00b0C and with a stoichiometric amount of HCHO. A concentrated feed of furfural as high as 40\u2009wt% in guaiacol can be employed without impacting the reaction selectivity, leading to an improvement of the reactor productivity to about 25\u2009kg\u2009m<jats:sup>\u22123<\/jats:sup>\u2009h<jats:sup>\u22121<\/jats:sup>. The recovery of the reaction products and the recycling of the <jats:italic>N,N<\/jats:italic>\u2010dimehylhydrazone are also discussed.<\/jats:p>","DOI":"10.1002\/cssc.202500318","type":"journal-article","created":{"date-parts":[[2025,3,25]],"date-time":"2025-03-25T20:19:07Z","timestamp":1742933947000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["<i>N,N<\/i>\u2010Dimethylhydrazine as a Reversible Derivatization Agent to Promote the Hydroxymethylation of Furfural with Formaldehyde"],"prefix":"10.1002","volume":"18","author":[{"given":"Sarah","family":"Behloul","sequence":"first","affiliation":[{"name":"Institut de Chimie des Milieux et Mat\u00e9riaux de Poitiers Universit\u00e9 de Poitiers CNRS  1 rue Marcel Dor\u00e9 86073 Poitiers France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zhen","family":"Yan","sequence":"additional","affiliation":[{"name":"Eco\u2010Efficient Products and Process 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