Cellulose-Derived Levoglucosenone, a Great Versatile Chemical Platform for the Production of Renewable Monomers and Polymers

Fadlallah, Sami; Mouterde, Louis M. M.; Garnier, Gil; Saito, Kei; Allais, Florent

doi:10.1021/bk-2020-1373.ch005

Cited by 20 publications

(37 citation statements)

References 51 publications

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“…Levoglucosenone (LGO) is a commercial and renewable chiral molecule that can be obtained at a ton/year scale from cellulosic waste (e.g., sawdust, straw and bagasse) (Figure 1) [4,5]. The great versatility of LGO in diverse synthetic processes [6], such as polymer syntheses [7], has been recently highlighted. Polymers with tailored structures and a wide range of properties, e.g., glass transition (T g ), are now accessible from LGO [7].…”

Section: Introductionmentioning

confidence: 99%

“…The great versatility of LGO in diverse synthetic processes [6], such as polymer syntheses [7], has been recently highlighted. Polymers with tailored structures and a wide range of properties, e.g., glass transition (T g ), are now accessible from LGO [7]. For instance, polyacetals with high T g (up to 100 • C) were prepared through the ring-opening metathesis polymerization (ROMP) of levoglucosenol (the reduced derivative of LGO) [8], and the cationic ring-opening polymerization (CROP) of the methylated analog of levoglucosenol [9].…”

Section: Introductionmentioning

confidence: 99%

“…Molecules 2021, 26, x 2 of 15 transition (Tg), are now accessible from LGO [7]. For instance, polyacetals with high Tg (up to 100 °C) were prepared through the ring-opening metathesis polymerization (ROMP) of levoglucosenol (the reduced derivative of LGO) [8], and the cationic ring-opening polymerization (CROP) of the methylated analog of levoglucosenol [9].…”

Section: Introductionmentioning

confidence: 99%

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Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation

et al. 2021

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Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free treatment of HBO-citro with NaBH4 at room temperature led to the full reduction of the lactone moiety which gave a novel fully renewable triol monomer having a citronellol side chain (Triol-citro). Noticeably, by simply changing the reducing agent, temperature and reaction duration, the partial reduction of HBO-citro can be achieved to yield a mixture of 5- and 6-membered Lactol-citro molecules. Triol-citro was chosen to prepare functional renewable polyesters having citronellol pendant chains via polycondensation reactions with diacyl chlorides having different chain lengths. Good thermal stability (Td5% up to 170 °C) and low glass transition temperatures (as low as −42 °C) were registered for the polyesters obtained. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan® 50 BG) to assess their biodegradability. A higher degradation profile was found for the polyesters prepared using co-monomers (acyl chlorides) having longer chain lengths. This is likely due to the decreased steric hindrance around the ester bonds which allowed enhanced accessibility of the enzyme.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation

et al. 2021

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“…E factor, which represent how many kgs of waste are produced for a kg of product, is nowadays largely accepted as a useful and simple measure to rapidly give an idea on the sustainability of a chemical reaction. 3,[37][38][39] Although many conditions describing the allylation of vanillin with K2CO3 and allyl bromide were reported in the literature, only the reaction conditions with the best yield and E factor are detailed in the table 6. While DMF was the best liquid additive for the allylation of vanillin in a ball-mill (furnishing allylated vanillin in 95% isolated yield), less problematic solvents such as acetone and ethanol provided better yields when used under classical stirring conditions (100% and 98%, Table 6, entries 1 and 2, respectively).…”

Section: Iii) Scale-up and Benchmarkingmentioning

confidence: 99%

Sustainability and efficiency assessment of lignin-derived phenolic synthons’ allylation: in solution versus ball-milling

Breilly

Fadlallah

FROIDEVAUX³

et al. 2022

Preprint

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Allylation of phenols, a widely used reaction in multistep synthetic pathways, was herein investigated using mechanochemistry. This synthesis was first optimized on vanillin by varying key parameters including both chemical (e.g., stoichiometry, reaction time, liquid additive) and mechanical (e.g., rotational speed, material, size and number of beads) conditions, leading to the isolation of allylated vanillin at the gram scale in excellent yield (95%). The optimized procedure was also successfully implemented to another bio-based phenol of interest, ethyl ferulate (92% isolated yield). The environmental impact of these procedures was compared with more classical in-solution protocols by calculating E factors, clearly indicating the superiority of the ball-milling approach over the solution-based procedures. Thus, the present work demonstrates that mechanochemistry is a versatile, efficient and waste-less method for the allylation of biobased phenols such as vanillin and ethyl ferulate.

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“…Given our strong expertise in levoglucosenone (LGO), a wood-based functional molecule produced at the scale of several tons per year [ 28 , 29 , 30 ], we have recently become interested in developing not only renewable functional monomers and polymers from LGO [ 31 , 32 , 33 , 34 , 35 , 36 ] but also biodegradation protocols to evaluate the end-of-life of our in-house corresponding materials. In this context, we recently reported the first fully renewable citronellol-containing monomers from LGO [ 34 , 35 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Enzymatic Degradation of Sustainable Levoglucosenone-Derived Copolyesters with Renewable Citronellol Side Chains

et al. 2022

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Recently, a renewable five-membered lactone containing citronellol (HBO-citro) was synthesized from levoglucosenone (LGO). A one-pot two-step pathway was then developed to produce a mixture of 5- and 6-membered Lactol-citro molecules (5ML and 6ML, respectively) from HBO-citro. Proton nuclear magnetic resonance (1H NMR) of a mixture of 5ML and 6ML at varying temperatures showed that the chemical shifts of the hydroxyls, as well as the 5ML:6ML ratio, are temperature-dependent. Indeed, a high temperature, such as 65 °C, led to an up-field shielding of the hydroxyl protons as well as a drop in the 5ML:6ML ratio. The monomers 5ML and 6ML were then engaged in polycondensation reactions involving diacyl chlorides. Renewable copolyesters with low glass transition temperatures (as low as −67 °C) and cross-linked citronellol chains were prepared. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan® 50 BG). A higher degradation rate was found for the polymers prepared using Lactol-citro molecules, compared to those obtained by the polycondensation reactions of diacyl chlorides with Triol-citro—a monomer recently obtained by the selective reduction of HBO-citro.

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Cellulose-Derived Levoglucosenone, a Great Versatile Chemical Platform for the Production of Renewable Monomers and Polymers

Cited by 20 publications

References 51 publications

Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation

Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation

Sustainability and efficiency assessment of lignin-derived phenolic synthons’ allylation: in solution versus ball-milling

Synthesis and Enzymatic Degradation of Sustainable Levoglucosenone-Derived Copolyesters with Renewable Citronellol Side Chains

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