Download - CoSMoS 2013 Eutectic Solvents Douglas Raynie
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Explorations With Deep Eutectic Solvents For Chemical Extractions
Douglas E. Raynie
Department of Chemistry and Biochemistry South Dakota State University [email protected]
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Green Chemistry
Supercritical Fluid
Technology
Analytical Separations Bioprocessing
Chemical Problem Solving
Environmental Analysis
Fundamental Studies
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DIFFUSION COEFFICIENT SUMMARY
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DECREASING THE IMPACT OF SOLVENTS 1.Reduce the volume of solvent
use higher concentra/ons use solvent for more than one step
2. Make the solvents greener
carefully chosen conven/onal solvents new green solvents
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GREEN SOLVENTS
We know guidelines such as like dissolves like, but when it comes to green solvents, how will we
recognize one when we see it?
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General Guidelines for PredicHng the Toxicity of Solvents As the number of alipha/c carbons increases, toxicity increases up to about eight carbons. Including subs/tu/ons, toxicity increases as molecular weight increases up to eight carbons. As the number of carbon-carbon double bonds increases, toxicity increases. As the degree of halogena/ons increases, toxicity increases. Brominated compounds are more toxic than chlorinated, which are more toxicity than uorinated. These same general statements are true for alipha/c subs/tu/on on aroma/c compounds. Subs/tu/on of aroma/cs increases toxicity. Subs/tu/on on phenols para- or ortho-, para- to the hydroxyl are more toxic.
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PROPERTIES OF CONCERN For greenness boiling point/energy to dis/ll ash point cumula/ve energy demand For uHlity polarity basicity/hydrogen-bond accep/ng ability acidity/hydrogen-bond dona/ng ability viscosity
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C. Capello, U. Fischer, and K. Hungerbuhler, Green Chem., 9, 927-934 (2007).
WHAT IS A GREEN SOLVENT?
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GSK SOLVENT SELECTION GUIDE
C. Jimenez-Gonzalez, A. D. Curzons, D. J. Constable, and V. L. Cunningham, J. Clean Technol. Environ. Policy, 7, 42-50 (2005).
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PFIZER MEDICINAL CHEMISTRY SOLVENT SELECTION GUIDE
Preferred Usable Undesirable
Water Cyclohexane Pentane Acetone Toluene Hexane(s)
Ethanol Methylcyclohexane Di-isopropyl ether 2-Propanol TBME Diethyl ether
1-Propanol Isooctane Dichloromethane Heptane Acetonitrile Dichloroethane
Ethyl acetate 2-Me THF Chloroform Isopropyl acetate THF NMP Methanol Xylenes DMF
MEK DMSO Pyridine 1-Butanol Acetic acid DMAc
t-Butanol Ethylene glycol Dioxane Dimethoxyethane
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PFIZER SOLVENT REPLACEMENT TABLE Red Solvents Alternative
Pentane Heptane Hexane(s) Heptane Di-isopropyl ether or ether 2-MeTHF or t-Butyl methyl ether Dioxane or dimethoxyethane 2-MeTHF or t-Butyl methyl ether Chloroform, dichloroethane or carbon tetrachloride
DCM
DMF, NMP or DMAc Acetonitrile Pyridine Et3N (if pyridine used as base) DCM (extractions) EtOAc, MTBE, toluene, 2-MeTHF DCM (chromatography) EtOAc/Heptanes Benzene Toluene
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Deep Eutectic Solvents (DES)
Diagrammatic representation of how HBD interacts with a QAS
Eutectic mixtures of quaternary ammonium salts (QAS) and hydrogen bond donors (HBD)
Bulky cations and smaller anions which are bound to a HBD
Abbott, A. P.; Boothby, D et al.; J. Am. Chem. Soc., 2004, 126 (29), 9142-9147.
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Choline chloride-Urea (1:2) Choline chloride melts at
302C and urea melts at 133C Molar ratio of choline chloride
to urea is 1:2 The eutectic mixture melts at
12C The depression in freezing
point is 178C
Andrew P. Abbott.; Glen Capper et al.; Chem. Eur. J., 2004, 10, 3769-3774
Choline chloride-Urea
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Synthesis General formula
(R1R2R3R4N+) (X-) (R5) (YH) A B C D 106 combinations Not possible to study all the combinations QAS: HBD: Choline chloride Acetylcholine chloride Urea Glycerol
N+
HO
Cl- N+
O
O
Cl-H2N
O
NH2
OH
HO
OH
Andrew P. Abbott.; Glen Capper et al.; Chem. Eur. J., 2004, 10, 3769-3774
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Synthesis 16 different combinations of DES were synthesized by
changing the QAS, HBD, and their composition Binary:
QAS+HBD (4 combinations)
Ternary:
QAS+HBD+HBD (6 combinations)
QAS+QAS+HBD (6 combinations)
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Components Composition Choline chloride: Urea 1:2
Choline chloride: Glycerol 1:2
Acetyl choline chloride: Urea 1:2
Acetyl choline chloride: Glycerol 1:2
Choline chloride: Urea: Glycerol 1:1:1
Choline chloride: Urea: Glycerol 2:3:1
Choline chloride: Urea: Glycerol 2:1:3
Acetyl choline chloride: Urea: Glycerol 1:1:1
Acetyl choline chloride: Urea: Glycerol 2:3:1
Acetyl choline chloride: Urea: Glycerol 2:1:3
Choline chloride: Acetyl choline chloride: Urea 1:1:4
Choline chloride: Acetyl choline chloride: Urea 1:2:6
Choline chloride: Acetyl choline chloride: Urea 2:1:6
Choline chloride: Acetyl choline chloride: Glycerol 1:1:4
Choline chloride: Acetyl choline chloride: Glycerol 1:2:6
Choline chloride: Acetyl choline chloride: Glycerol 2:1:6
QAS+HBD (4combinations)
QAS+HBD+HBD (6 combinations)
QAS+QAS+HBD (6 combinations)
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Phase Properties
Tc range from -37C to -15C Tm range from 12C to 25C Tc and Tm values of DES were far less than the
corresponding QAS and HBD used in their synthesis Tdecomp (10%) range from 186C to 208C
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Viscosity Range from 5.4294 x 10-1 Pa.sec to 0.9243 x 10-2 Pa.sec As the choline chloride concentration increased, viscosity
decreased Viscosity studied as a function of temperature from 25C
-150C, with increasing temperature viscosity decreased
Range from 1.1684 g/mL to 1.264 g/mL As the glycerol concentration increased, density increased
Density
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pH
Range from 10.44 to 5.42 As the acetylcholine chloride concentration increased, pH
decreased As the urea concentration increased, pH increased
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Kow Range from 0.061 to 0.141 As the glycerol concentration increased, Kow increased
RefracHve Index
Ranges from 1.43-1.51 Relates to polarity (water is 1.33)
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Choline Chloride
Urea
Glycerol
1:2 Choline Chloride: Urea
1:2 Choline Chloride: Glycerol
1:1:1 Choline Chloride:Urea: Glycerol
Water S S S S S S
Acetone IS IS IS IS IS IS
Acetonitrile IS IS IS IS IS IS
Methanol S S S S S S
Ethanol S S S S S S
Isopropanol IS IS S IS S IS
Dichloromethane IS SS IS IS IS IS
Chloroform SS SS IS IS IS IS
DMSO SS S S S S S
Pentane IS IS IS IS IS IS
Hexane IA IS IS IS IS IS
Toluene IS IS IS IS IS S
Miscibility with Common Solvents
S= soluble SS = slightly soluble IS = insoluble
DES soluble with polar solvents
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*
Cyclohexane 0 0 0
Benzene 0 0.1 0.59
Acetonitrile 0.19 0.31 0.75
Water 1.17 0.47 1.09
1:2 Choline Chloride:Urea
0.734 0.632 0.987
1:2 Choline Chloride:Glycerol
0.927 0.642 0.979
1:1:1 Choline Chloride:Urea:Glycerol
0.917 0.765 0.985
= acidity, H-bond dona/ng ability = basicity, H-bond accep/ng ability * = polarity and polarizability
Kamlet-TaQ Solvatochromic Parameters
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DES
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DES
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DES
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DES
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Dissolution of Sugars
Glucose Sucrose Dextrose Xylose
1:2 Choline chloride: Urea
Soluble Soluble Soluble Soluble
1:2 Choline chloride: Glycerol
Soluble Soluble Soluble Soluble
1:2 Acetyl choline chloride: Urea
Soluble Soluble Soluble Soluble
1:2 Acetyl choline chloride: Glycerol
Soluble Soluble Soluble Soluble
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Naturally Occurring DES 1:2, 1:3 Citric Acid:Choline Chloride 1:1, 1:2, 1:3 Malic Acid:Choline Chloride 1:1, 1:2, 1:3 Maleic Acid:Choline Chloride 1:1 Aconi/c Acid:Choline Chloride 1:1:1 Glucose:Choline Chloride:Water 1:1:1 Fructose:Choline Chloride:Water 1:1:1 Sucrose:Choline Chloride:Water 1:1, 1:2, 1:3 Citric Acid:Proline 1:1 Malic Acid:Glucose 1:1 Malic Acid:Fructose 1:1 Malic Acid:Sucrose 2:2 Citric Acid:Glucose 2:1 Citric Acid:Trehalose 1:1 Citric Acid:Sucrose
4:1 Maleic Acid:Glucose 1:1 Maleic Acid:Sucrose 1:1 Glucose:Fructose 1:1 Fructose:Sucrose 1:1 Glucose:Sucrose 1:1:1 Sucrose:Glucose:Fructose
Plant Physiology 156: 1701-1705 (2011).
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Analy.cal Chemistry 85: 6272-6278 (2013).
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CONCLUSIONS
Deep eutec/c solvents comprise a class of novel, green solvents suitable for separa/ons and other chemical processes.