journal article·2025-07-15Open access

Upgrading Renewable Phenols to Functional Benzyl Chlorides and Formamides: Versatile Building Blocks for the Chemical Industry

Nicola Porcelli, Biagio Anderlini, Alberto Ughetti, Mattia Giuliana, Matteo Fiocchi, Fabrizio Roncaglia

Applied Sciences· Volume 15· Issue 14

Abstract

A reliable synthetic method based on the already known Blanc–Quelet methodology has been developed for upgrading bio-based phenols into valuable electrophilic mono-, di-, and trifunctional benzyl chlorides. These compounds show significant potential as building blocks for polymer production and the synthesis of specialty chemicals. As an example of their applicability, their direct interaction with formamide has been evaluated, obtaining an effective transformation towards the corresponding N-formylamides. These compounds represent versatile synthetic precursors to a variety of functionalized targets.
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Research context

OpenAlex topics: Microbial Natural Products and Biosynthesis · Catalysis for Biomass Conversion · Carbon dioxide utilization in catalysis

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Via Campi 103, 41125 Modena, Italy

National Interuniversity Consortium of Materials Science and Technology (INSTM), Via G. Giusti 9, 50121 Firenze, Italy

Interdepartmental Centre H2-MORE, University of Modena and Reggio Emilia, Via Università 4, 41125 Modena, Italy

References (53)

Show source-provided references
1. Bio-Renewable Polymers Based on Lignin-Derived Phenol Monomers: Synthesis, Applications, and Perspectives10.1002/sus2.87 ↗
2. Recent Advances in the Catalytic Depolymerization of Lignin towards Phenolic Chemicals: A Review10.1002/cssc.202001213 ↗
3. Sarika, P.R., Nancarrow, P., Khansaheb, A., and Ibrahim, T. (2020). Bio-Based Alternatives to Phenol and Formaldehyde for the Production of Resins. Polymers, 12.10.3390/polym12102237 ↗
4. Naturally Occurring Phenolic Sources: Monomers and Polymers10.1039/C4RA00181H ↗
5. From Plant Phenols to Novel Bio-Based Polymers10.1016/j.progpolymsci.2021.101473 ↗
6. Chemical Modification of Lignins: Towards Biobased Polymers10.1016/j.progpolymsci.2013.11.004 ↗
7. Epoxy Thermosets and Materials Derived from Bio-Based Monomeric Phenols: Transformations and Performances10.1016/j.progpolymsci.2020.101287 ↗
8. Martínková, L., Grulich, M., Pátek, M., Křístková, B., and Winkler, M. (2023). Bio-Based Valorization of Lignin-Derived Phenolic Compounds: A Review. Biomolecules, 13.10.3390/biom13050717 ↗
9. Minireview: Recent Efforts toward Upgrading Lignin-Derived Phenols in Continuous Flow10.1007/s41981-022-00248-8 ↗
10. Toward Mild Synthesis of Functional Chemicals from Lignin-Derived Phenolics via Emerging Catalytic Technology
11. Su alcuni derivati clorurati del triossimetilene
12. LIV.—The Introduction of the Chloromethyl Group into the Aromatic Nucleus10.1039/CT9201700510 ↗
13. Sur La Préparation de Dérivés Chlorométhyléniques Aromatiques
14. Preparation d’un Derive Chloro-Methyl Du Para-Bromo-Anisol (Methoxy-2 Bromo-2 α-Chlorotoluene)
15. Aromatic Substitution. XXXVIII. Chloromethylation of Benzene and Alkylbenzenes with Bis(Chloromethyl)Ether, 1,4-Bis(Chloromethoxy)Butane, 1-Chloro-4-Chloromethoxybutane, and Formaldehyde Derivatives10.1021/jo00871a032 ↗
16. Towards Halomethylated Benzene-Bearing Monomeric and Polymeric Substrates10.1163/138577211X557495 ↗
17. Structural Identification of Products from the Chloromethylation of Salicylaldehyde
18. Transition-Metal-Free, General Construction of Thioamides from Chlorohydrocarbon, Amide and Elemental Sulfur10.1002/ejoc.202100588 ↗
19. Light on the Sustainable Preparation of Aryl-Cored Dibromides10.3762/bjoc.20.95 ↗
20. Incorporation of Phenolic Skeleton into Imidazolium Ionic Polymers as Recyclable Catalysts for Efficient Fixation of CO2 into Cyclic Carbonates10.1016/j.cej.2023.148359 ↗
21. Ramachandran, P.V., Alawaed, A.A., and Singh, A. (2023). Titanium-Mediated Reduction of Carboxamides to Amines with Borane–Ammonia. Molecules, 28.10.3390/molecules28124575 ↗
22. Nickel-Catalyzed Amination of Aryl Chlorides with Amides10.1021/acs.orglett.0c03836 ↗
23. Selective Room-Temperature Hydrogenation of Amides to Amines and Alcohols Catalyzed by a Ruthenium Pincer Complex and Mechanistic Insight10.1021/acscatal.0c01406 ↗
24. A More Sustainable and Highly Practicable Synthesis of Aliphatic Isocyanides10.1039/C9GC04070F ↗
25. Isocyanide 2.010.1039/D0GC02722G ↗
26. Isocyanide Chemistry Enabled by Continuous Flow Technology10.1039/D2RE00454B ↗
27. Formamides as Isocyanate Surrogates: A Mechanistically Driven Approach to the Development of Atom-Efficient, Selective Catalytic Syntheses of Ureas, Carbamates, and Heterocycles10.1021/jacs.9b08942 ↗
28. Dehydrogenative Synthesis of Carbamates from Formamides and Alcohols Using a Pincer-Supported Iron Catalyst10.1021/acscatal.1c02718 ↗
29. Manganese-Catalyzed Dehydrogenative Synthesis of Urea Derivatives and Polyureas10.1021/acscatal.2c00850 ↗
30. Isocyanate-Free Synthesis of Ureas and Polyureas via Ruthenium Catalyzed Dehydrogenation of Amines and Formamides10.1002/app.52088 ↗
31. One-Pot Synthesis of Thiocarbamates10.1002/ejoc.202100858 ↗
32. Iron-Catalyzed Reductive Strecker Reaction10.1016/j.jcat.2021.01.003 ↗
33. Practical Synthesis of Tetrazoles from Amides and Phosphorazidates in the Presence of Aromatic Bases10.1016/j.tet.2022.132642 ↗
34. A Facile Direct Route to N-(Un)Substituted Lactams by Cycloamination of Oxocarboxylic Acids without External Hydrogen10.1002/cssc.201901780 ↗
35. Über Die Chlormethylierung Des O- Und Novo-vanillins Und Die Gewinnung von 4-Hydroxy-5-alkoxy-isophthalaldehyden10.1002/ardp.19652980303 ↗
36. The One-Pot Halomethylation of 5-Substituted Salicylaldehydes as Convenient Precursors for the Preparation of Heteroditopic Ligands for the Binding of Metal Salts10.1016/j.tetlet.2006.09.149 ↗
37. Continuous Flow Preparation of Benzylic Sodium Organometallics10.1002/anie.202203807 ↗
38. An Inexpensive and Convenient for Chloromethylation of Aromatic Hydrocarbons by Phase Transfer Catalysis in Aqueous Media10.4067/S0717-97072010000100023 ↗
39. Formamide Reaction Network in Gas Phase and Solution via a Unified Theoretical Approach: Toward a Reconciliation of Different Prebiotic Scenarios10.1073/pnas.1512486112 ↗
40. Synthesis of a TNF Inhibitor, Flurbiprofen and an i-Pr Analogue in Enantioenriched Forms by Copper-Catalyzed Propargylic Substitution with Grignard Reagents10.1039/D1OB01944A ↗
41. Vanillin Production from Lignin: Rigorous Process Simulation Results for Ethyl Acetate versus Aliphatic-Alcohol-Specific Process Designs10.1016/j.clet.2021.100133 ↗
42. Fuson, R.C., and McKeever, C.H. (2011). Chloromethylation of Aromatic Compounds. Organic Reactions, John Wiley & Sons, Ltd.10.1002/0471264180.or001.03 ↗
43. Picein and Piceol Concentrations in Norway Spruce10.1016/0147-6513(90)90032-Z ↗
44. Novel Biobased Epoxy Resin Thermosets Derived from Eugenol and Vanillin10.1016/j.polymdegradstab.2018.12.007 ↗
45. Selective Production of Guaiacol from Lignin via Catalytic Transfer Hydrogenolysis Using Ru-Cu/Zirconia
46. Process Optimization and Extraction of Acids, Syringols, Guaiacols, Phenols and Ketones from Beech Wood Slow Pyrolysis Liquids with Supercritical Carbon Dioxide at Different Densities10.1016/j.supflu.2023.105937 ↗
47. Wood-Derived Phenol Novolaks and Their Wood/Epoxy Biocomposites10.1002/app.41347 ↗
48. Microwave-Assisted Solvent-Free Synthesis of Novel Benzoxazines: A Faster and Environmentally Friendly Route to the Development of Bio-Based Thermosetting Resins10.1002/pola.28755 ↗
49. Bruckner, R., and Harmata, M. (2010). Kinetic Aspects of Ar-SE Reactions: Reactivity and Regioselectivity in Reactions of Electrophiles with Substituted Benzenes. Organic Mechanism—Reactions, Stereochemistry and Synthesis, Springer.
50. Decomposition Characteristics of Softwood Lignophenol under Hydrothermal Conditions10.1016/j.biombioe.2010.12.040 ↗
51. Hazardous Compounds in Tobacco Smoke10.3390/ijerph8020613 ↗
52. Alkylation of p-Cresol with Tert-Butyl Alcohol Using Benign Bronsted Acidic Ionic Liquid Catalyst10.1016/j.molcata.2010.01.016 ↗
53. Synthesis of 2,6-Dihydroxymethyl-4-Methyl Phenol and Its Application in Novolac Resins10.2494/photopolymer.27.545 ↗