1 / 20

Sustainable Chemical Transformations with Non-conventional Solvents

Explore environmentally friendly chemical transformations based on non-conventional solvents such as ionic liquids and fatty esters. Learn about selective absorption, enzymatic transformations, and organocatalyzed dihydroxylation in water. Discover the advantages of using these innovative solvents for efficient catalyst reuse and product separation.

tobyc
Download Presentation

Sustainable Chemical Transformations with Non-conventional Solvents

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. Nuno Lourenço Andreia Rosatella Carlos Monteiro Prashant Kulkarni Luís Branco Carlos Afonso More Environmentally Friendly Chemical Transformations Based on Non-conventional Solvents Transformações Químicas Mais Sustentáveis Baseadas em Solventes Não Convencionais Carlos A. M. Afonso, Luís C. Branco, Carlos Monteiro, Nuno Lourenço, Andreia A. Rosatella, Prashant Kulkarni CQFM Centro de Química-Física Molecular and IN – Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Lisbon, Portugal

  2. Presentation Outline • Introduction; • Selective Absorption of Organic Vapours by Ionic Liquids; • Sharpless asymmetric dihydroxylation of olefins without chiral ligand by using chiral ionic liquids; • Enzymatic Transformation: EKR using fatty esters; • Organocatalyzed dihydroxylation of olefins in water.

  3. Examples Using Non-conventional Solvents Ionic Liquids Fatty Ester (Biodiesel Component) Water

  4. General Properties of Ionic Liquids • Almost Negligible Vapour Pressure; • High Thermal Stability (over 300 oC); • High Ionic Conductivity; • Large Electrochemical Window; • Non-soluble in scCO2; • Adjustable Solubility of scCO2, Organic Compounds and Transition Metal Complexes in the Ionic Liquid; • Adjustable Solubility of the Ionic Liquid in Water, Alkyl Ethers and Alkanes.

  5. Selective Absorption of Organic Vapours by Ionic Liquids • Key Properties of the ionic liquid in this process: • Selective affinity of organic molecules to the ionic liquid; • Non-volatility of the ionic liquid.

  6. Dioxins Capture by ILs Less Toxic Dioxins Tested Example of absorption of dioxin 1, 2 and 3 in [C8mim][dca] (48 h, 100 OC) • High efficient dioxin capture, including in case of immobilized in wood fly ash • Complete desorption of dioxins from ILs • Possibility to reuse the IL P. S. Kulkarni, L. C. Branco, J. G. Crespo, C. A. M. Afonso, Environmental Science & Technology, 2008,42, 2570; Portuguese patent pending(103717B (13/04/2007)

  7. Dioxins Capture by Ionic Liquids Absorption Apparatus 1&2) Sand bath; 3) thermometer; 4) glass chamber; 5) lid; 6) glass vials containing ionic liquid and stirrer bar; 7) a glass vial containing dioxin compound 1) a glass vial containing ionic liquid and stirrer bar; 2) a glass vial containing the dioxin immobilized in wood burned fly ash 1) Forced air circulated oven; 2 ) sand bath; 3) thermometer; 4) stirrer. Desorption Apparatus 1) Glass chamber; 2) glass vials containing the ionic liquid after absorption of dioxin gas; 3) low temperature trap

  8. Catalyst Reuse and Products Separation Efficient catalyst reuse by simple dissolution in non-conventional media, C. A. M. Afonso, L. C. Branco, N. R. Candeias, P. M. P. Gois, N. M. T. Lourenço, N. M. M. Mateus, J. N. Rosa, Chem. Comm,2007, 2669-2679 Feature Article

  9. Sharpless Asymmetric Dihydroxylation • Key properties of the ionic liquid in this transformation: • Solubility of the catalytic system in the ionic liquid; • Low solubility of IL in the organic solvent or in scCO2; • Ionic liquid as efficient reaction media; • Chiral ionic liquid acts as asymmetric inducting agent.

  10. Chiral ionic liquids based on the guanidinium [dmg] cation L. C. Branco, P. M. P.Gois, N. M. T. Lourenço, V. B. Kurteva, C. A. M. Afonso Chem. Comm.2006, 2371

  11. New Asymmetric Dihydroxylation (AD) Based on CILs vs Sharpless Methodology

  12. Reuse of the AD Catalytic System Using[(di-h)2dmg][quinic]as Co-Solvent

  13. Enzymatic Transformation: EKR Enzymatic Resolution and Separation of sec Alcohols Using Fatty Esters (Biodiesel Component) as Reaction Medium and Anchoring Agent • Key properties of the ionic liquid in this process: • High efficiency of the enzyme in the fatty ester medium; • Low-volatility of the fatty ester allows the continuous removal of ethanol from the enzymatic transterification.

  14. Advantages of this Approach ENZYME FATTY ESTER DISTILLATION REUSABLE REACTION SYSTEM

  15. Enzymatic Transformation: EKR Fatty ester (biodiesel component) as acylating agent and reaction medium The use of fatty esters as an enzymatic anchoring agent for resolution of sec-alcohols was claimed by Negishi et al,in a patent: Nisshin Oil Mills, Ltd, EP 0709 465 A2 (1995)

  16. EKR of 1-Phenylethanol Using Fatty Ester Cycle 1 Cycle 2 Cycle 3 All reactions were carried out using 10 mmol alcohol, 10 mmol of fatty ester and 500 mg of CAL B

  17. Organocatalyzed dihydroxylation of olefins in water • Key properties of the catalytic system in this transformation: • Solubility of the catalyst in water; • Low solubility of the catalyst in the organic solvent; • low volatility of the catalyst.

  18. Dihydroxylation of olefins in water catalyzed by p-TsOH: Catalyst reuse Catalyst reuse: Isolation of cyclohexanediol by extration with diethyl ether and recovery of p-TsOH by aqueous phase evaporation

  19. Commercialization of Ionic Liquids www.solchemar.com Laboratory Based Company Development of Spectroscopic High Pure Ionic Liquid Available up to 70 ionic liquids based on the following salts: General Purity Grade Exclusive Solchemar Purity Grade Magnetic Ionic Liquids Chiral Ionic Liquids

  20. Acknowledgements Ionic Liquids Ionic Liquids ACS Green Chemistry Institute Petroleum Research Fund (GCI-PFR) Grant 49150-GCI www.solchemar.com www.solchemar.com Ionic Liquids CYTEC Thank you for your kindly attention

More Related