Catalytic Routes to Produce Polyphenolic Esters (PEs) from Biomass Feedstocks
Abstract
:1. Introduction: Properties and Potential Applications of Polyphenolic Esters
2. Methodology
3. Synthesis of Polyphenolic Esters through Bio-Catalysis
3.1. Enzymatic Synthesis of Polyphenolic Esters from Flavonoids
3.2. Enzymatic Synthesis of Polyphenolic Esters from Polyphenolic Acids and Alcohols
3.3. Enzymatic Synthesis of Polyphenolic Esters from Biomass Extracts
3.4. Main Aspects on the Currently Used Reactors for Polyphenolic Esters Production
4. Chemical Synthesis of Polyphenolic Esters
Polyphenolic Esters Synthesis by Acid Catalysis
Polyphenol | Reagent/Catalyst | Reaction Condition | Reference |
---|---|---|---|
4-methoxy cinnamic acid | Alcohol (1 eq): Glycerol Homogeneous catalysts (6 mol%): P-TSA | 110 °C, 2 h Yield: 20% | [109] |
Caffeic acid | Alcohol (10 eq.): Glycerol Homogeneous catalysts (10% relative to the weight of all substrates): Ionic liquids, H2SO4 P-TSA | 90 °C, 2 h Yield: 10–95% | [110] |
Alcohol (3 eq.): Glyceryl monoleate Heterogeneous catalysts (10% w/w): Solid acids (A-15, A-35, NKC-9, SO42−/ZrO2 and SO42−/Fe2O3) | 100 °C, 36 h Conversion: 5–38% | [32] | |
Deep eutectic solvent consisting of choline chloride and Caffeic acid | Alcohol (3 eq.): Glyceryl monoleate Heterogeneous catalysts (10% w/w): Solid acids (A-15, A-35, NKC-9, SO42−/ZrO2 and SO42−/Fe2O3) | 100 °C, 36 h Conversion: 5–87% | [32] |
Ethyl caffeate | Alcohol (10 eq.): Glycerol Homogeneous catalysts (10% relative to the weight of all substrates): Ionic liquids, SA P-TSA | 90 °C, 3 h Yield: 5–85% | [110] |
Ferulic acid | Alcohols (15 eq.): Glycerol Heterogeneous catalyst (14% w/w): A-35 | 90 °C, 7 h Yield: 98% | [111] |
Ethyl ferulate | Alcohol (10 eq): Glycerol Homogeneous catalysts (14% relative to the weight of all substrates): Ionic liquids, SA P-TSA | 80 °C, 10 mmHg, 14 h Yield: 5.5–98% | [108] |
5. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Polyphenol | Reagent/Catalyst | Reaction Condition | Reference |
---|---|---|---|
Hydroxytyrosol | Fatty acids (1/1 as mol of fatty acid/mol of polyphenol): octanoic acid Novozym 435 (40 mg) | 50 °C, 20 h, n-hexane Yield: 85–90% | [54] |
Ethyl fatty acid esters (30/1 as mol of ester/mol of polyphenol): octanoate, cis-5,8,11,14,17-eicosapentanoate, cis-4,7,10,13,16,19-docosahexanoate Novozym 435 (40 mg) | 37 °C, 4–16 h, vacuum Yield: 34–93% | [55] | |
Ethyl acetate (316/1 as mol of ester/mol of polyphenol) Novozym 435 (10 g/L) | 45 °C, 7 h, Yield: 98% | [56] | |
Ethyl octanoate (154/1 as mol of ester/mol of polyphenol) Novozym 435 (10 g/L) | 45 °C, 7 h, molecular sieves Yield: 78% | [56] | |
Ethyl octanoate (2/1 as mol of ester/mol of polyphenol) Novozym 435 (10 g/L) | 45 °C, 5 h, 2-methyl 2-butanol Yield: 69% | [56] | |
Fatty acids (2/1–5/1 as mol of fatty acid/mol of polyphenol): decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and eicosapentaenoic acid Novozym 435 (54% w/w) | 40–50 °C, 1–24 h, 2-methyl-2-butanol, tert-butanol, isooctane, diethyl ether, ethyl acetate Yield: 45.91–85.61% | [57] | |
Tyrosol | Methyl or ethyl esters (10 mL/1mmol of polyphenol): acetate, butyrate, laurate, palmitate, stearate, oleate and linoleate Novozym 435 (0.04% w/w) | 55 °C, 1.5–42 h, Yield: 60–92% | [58] |
Oleic acid (1 mol/1 mol of polyphenol) Novozym 435 (10% w/w relative to mixture) | 80 °C, 10 mbar, 2 h Yield: 95% | [59] | |
di-o-phenolic compounds | Ethyl fatty acid esters (30/1 as mol of ester/mol of polyphenol): palmitate, butyrate, stearate, octanoate and eicosapentaenoate Novozym 435 (40 mg) | 37 °C, 4–16 h, 5–10 mmHg Yield = 29–98% | [55] |
Fatty acids (2/1 as mol of fatty acid/mol of polyphenol): palmitic acid Novozym 435 (40 mg) | 37 °C, 16 h, 5–10 mmHg, acetonitrile Yield = 69–85% | [55] | |
2-(4-Hydroxyphenoxy) propionic acid | Alcohol: Octanol (large excess) Novozym 435 (37% w/w) | 52.9 °C, 58.2 h Yield = 95.9% | [60] |
4-Hydroxyphenylacetic acid | Alcohol (1/1 as mol of alcohol/mol of phenolic acid): octanol CALB (80 mg/mL) | 60 °C, 72 h, [BMIM]PF6 Yield = 62.6% | [61] |
Dihydrocaffeic acid | Alcohol (8/1 as mol of alcohol/mol of phenolic acid): linoleoyl alcohol Novozym 435 (25 mg) | 55 °C, 10 days, vacuum, Hexane/2-butanone (75/25 v/v) Yield: 99% | [62] |
Alcohols (3/1 as mol of alcohol/mol of phenolic acid): butanol, hexanol, octanol, dodecanol, octadecenol Novozym 435 (100 mg) | 60 °C, 3–5 d, Hexane/2-butanone (75/25 v/v), Molecular sieves Yield: 44–95% | [63] | |
Caffeic acid | Alcohol (3/1 as mol of alcohol/mol of phenolic acid): hexanol Novozym 435 (100 mg) | 60 °C, 5 d, Hexane/2-butanone (75/25 v/v), Molecular sieves Yield: 20% | [63] |
Ferulic acid | Alcohols (3/1 as mol of alcohol/mol of phenolic acid): hexanol Novozym 435 (100 mg) | 60 °C, 5 d, Hexane/2-butanone (75/25 v/v), Molecular sieves Yield: 5% | [63] |
Alcohols (1/1 as mol of alcohol/mol of phenolic acid): hexanol, octanol RML (80 mg/mL) | 60 °C, 3 d, [BMIM]PF6 Yield = 38.1% | [61] |
Polyphenol | Reagent/Catalyst | Reaction Condition | Reference |
---|---|---|---|
Dihydrocaffeic acid | Alcohols (30 eq.): propanol and hexanol Homogeneous catalyst (1 mol%): P-TSA | 80–90 °C, 2 h Yield: 88–99% | [95] |
Caffeic acid | Alcohols (30 eq.): propanol Homogeneous catalyst (1 mol%): P-TSA | 90 °C, 2 h Yield: 85% | [95] |
Alcohols (12 eq.): Octanol Homogeneous catalyst (20 mol%): SA | 100 °C, 2 h Yield: 67% | [96] | |
Alcohols (8 eq.): Octanol, decanol, myristyl alcohol, cetyl alcohol, stearyl alcohol Heterogeneous catalyst (5% w/w): A-35 | 85 °C, 12 h Conversion: 25–45% | [97] | |
Alcohol (5–50 eq.): ethylene glycol, 1,4-butanediol, 1,8-octanediol, 1,12-dodecanediol Homogeneous catalysts (3% w/w): SA | 90 °C, 2 h Yield: 30–80% | [98] | |
Deep eutectic solvent consisting of choline chloride and Caffeic acid | Alcohols (8 eq.): Octanol, decanol, myristyl alcohol, cetyl alcohol, stearyl alcohol Heterogeneous catalyst (5% w/w): A-35 | 85 °C, 12 h Conversion: 80–90% | [97] |
Ferulic acid | Alcohols (6 eq): methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol Homogeneous catalyst (10 mol%): SA | Reflux, 8–28 h Yield: 46–81%; Microwave irradiation (75–148 °C) 3–5 min Yield: 91–95% | [99] |
Alcohols (12 eq.): Octanol Homogeneous catalyst (20 mol%): SA | 100 °C, 3 h Yield: 81% | [96] | |
Gallic acid | Alcohol (30 eq): propanol Homogeneous catalyst (1 mol%): P-TSA | 90 °C, 2 h Yield: 88% | [95] |
Protocatechuic acid | Alcohols (154–285 eq): methanol, ethanol and propanol Homogeneous catalyst: SA | RT, 5 days Yield: 71–81% | [100] |
Sinapic acid | Alcohols (180–400 eq): methanol, ethanol, propanol and butanol Homogeneous catalyst: SA | RT, 5 days Yield: 79–94% | [28] |
Alcohols (12 eq.): Octanol Homogeneous catalyst (20 mol%): SA | 100 °C, 3 h Yield: 93% | [96] | |
Alcohol (5–50 eq.): ethylene glycol, 1,4-butanediol, 1,8-octanediol, 1,12-dodecanediol Homogeneous catalysts (3 % w/w) SA | 90 °C, 2 h Yield: 35–72% | [98] | |
Rosmarinic acid | Alcohols (200–2200 eq.): methanol, butanol, octanol, dodecanol, hexadecanol, octadecanol and eicosanol Heterogeneous catalyst (5% w/w): A-IR-120H | 55–70 °C, 4–21 days Yield: 82–99% | [101] |
Hydroxytyrosol | Ethyl or methyl esters (1/25 as mL of ester/mg of polyphenol): acetate, butyrate, laurate, palmitate, stearate, oleate and linoleate Homogeneous catalyst (9 mol%): P-TSA | RT, 24 h Yield: 65–86% | [102,103] |
Tyrosol | Methyl or ethyl esters (10 mL/1mmol of polyphenol): acetate, butyrate, laurate, palmitate, stearate, oleate and linoleate Homogeneous catalyst (6 mol%): P-TSA | 70 °C, 2–32 h Yield: 65–98% | [58] |
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Faggiano, A.; Ricciardi, M.; Proto, A. Catalytic Routes to Produce Polyphenolic Esters (PEs) from Biomass Feedstocks. Catalysts 2022, 12, 447. https://doi.org/10.3390/catal12040447
Faggiano A, Ricciardi M, Proto A. Catalytic Routes to Produce Polyphenolic Esters (PEs) from Biomass Feedstocks. Catalysts. 2022; 12(4):447. https://doi.org/10.3390/catal12040447
Chicago/Turabian StyleFaggiano, Antonio, Maria Ricciardi, and Antonio Proto. 2022. "Catalytic Routes to Produce Polyphenolic Esters (PEs) from Biomass Feedstocks" Catalysts 12, no. 4: 447. https://doi.org/10.3390/catal12040447