Green Solvents
Green Solvents
Green Solvents
net/publication/319871931
Green solvents
CITATIONS READS
0 2,451
1 author:
Agata Tarczykowska
Nicolaus Copernicus University
10 PUBLICATIONS 2 CITATIONS
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
All content following this page was uploaded by Agata Tarczykowska on 17 September 2017.
The journal has had 7 points in Ministry of Science and Higher Education parametric evaluation. Part B item 1223 (26.01.2017).
1223 Journal of Education, Health and Sport eISSN 2391-8306 7
© The Authors 2017;
This article is published with open access at Licensee Open Journal Systems of Kazimierz Wielki University in Bydgoszcz, Poland
Open Access. This article is distributed under the terms of the Creative Commons Attribution Noncommercial License which permits any noncommercial use, distribution, and reproduction in any medium,
provided the original author(s) and source are credited. This is an open access article licensed under the terms of the Creative Commons Attribution Non Commercial License
(http://creativecommons.org/licenses/by-nc/4.0/) which permits unrestricted, non commercial use, distribution and reproduction in any medium, provided the work is properly cited.
This is an open access article licensed under the terms of the Creative Commons Attribution Non Commercial License (http://creativecommons.org/licenses/by-nc/4.0/) which permits unrestricted, non commercial
use, distribution and reproduction in any medium, provided the work is properly cited.
The authors declare that there is no conflict of interests regarding the publication of this paper.
Received: 15.08.2017. Revised: 10.09.2017. Accepted: 10.09.2017.
Green solvents
Agata Tarczykowska1
1
Katedra i Zakład Chemii Leków, Wydział Farmaceutyczny, Collegium Medicum w
Bydgoszczy, Uniwersytet Mikołaja Kopernika w Toruniu, ul. dr. A. Jurasza 2, 85-089
Bydgoszcz
Abstract
Prolonged exposure to solvents has a harmful impact on all living organisms, damaging most
organs. Reducing the use of solvents or replacing them with less toxic ones, are two of the
most important ambitions of green chemistry. Water, supercritical fluids, ionic liquids, non-
toxic liquid polymers and their varied combinations are part of the class of green solvents.
They are characterized by low toxicity, convenient accessibility and possibility of reuse as
well as great efficiency.
224
Introduction
Concerns have arisen in the field of chemical processing since enormous amounts of
poisonous and inflammable solvents are used every day. Each year, more than twenty million
tons of waste residues from organic solvents are emitted to the atmosphere, causing
unnecessary waste of solvents and polluting the environment [1]. Despite the fact that organic
solvents, such as DMSO, DMF, acetone as well as aromatic ones e.g. benzene, toluene and
chlorinated solvents (CHCl) contribute to environmental pollution, they are still used in large
amounts [6]. Prolonged exposure to solvents has a harmful impact on all systems present in
living organisms, damaging mainly respiratory and nervous systems [6,3]. Moreover, the use
of hazardous solvents is deleterious to organs, e.g. carbon tetrachloride and chloroform are
hepatotoxic [2,4]. The kidney failure occurs while glycol ethers and chlorinated solvents are
used [2].
All facts mentioned above attract great interest among academia and industries for use of
green solvents.
225
Fig. 1. Major aims of green chemistry [24].
Green solvents
226
Fig. 3. Solvent selection guide for membrane fabrication [25].
Synthesis in water
Despite the fact that water causes many problems as a solvent in organic synthesis,
purification methods, and separating final products, in recent years it has become more
popular in organic reactions. In some cases, water stimulates reactions through a dissolution
of reagents and ensures selectivity. Moreover, oxygen is not soluble in water which can be an
advantage for metal catalysts. In last decade water has become a really popular solvent thanks
to its properties such as being harmless for the environment and it has been documented in
a large amount of papers [26-28].
It is known that water is the most used solvent in all biochemical reactions taking
place in nature [27]. Notwithstanding, water is a suitable solvent only for organic chemicals,
containing polar groups e.g. alcohols or carboxylic acids. However, two decades ago special
selectivity present in aqueous solutions was also observed in water suspensions, where one
soluble element interacted with a poorly soluble one [1,27,31]. Lately, many researchers have
observed an excellent acceleration of a reaction in such a suspension, named by them:
reactions on water [27,29,30]. It would be an understatement to say that water is just an
environmentally friendly solvent, it possesses exceptional properties that are substantially
unique, associated to the hydrophobic effect [27].
227
Supercritical carbon dioxide and supercritical water
Lately, ionic liquids received a lot of attention from scientists due to their unique
properties and abilities [34]. Ionic liquids consist of a mixture of cations and anions, molten
salts. Their melting points reach 100ºC which makes them a great alternative to convenient
solvents in organic syntheses. Most often they possess quaternary ammonium cations and
inorganic anions. Despite this fact, ionic liquids do not precisely meet all “green” conditions,
they are still quite promising alternative solvents [26].
There is a wide range of applications that ionic liquids are used for. They have been
used for battery production, lubricants, plasticizers, solvents, mass spectrometry matrices,
solvents for nanomaterials production, extraction reactions, gas absorption agents and among
other things [35].
They are non-volatile and non-flammable hence they could work in high-vacuum
systems and exclude possible contaminants. Ionic liquids do not form a homogeneous mixture
with many organic solvents and produce an anhydrous polar alternate option for two-phase
systems. Additionally, they may provide immiscible polar phases with water, when they are
hydrophobic [36].
228
Non-toxic liquid polymers
Liquid polymers comprise a group of non-volatile solvents that gained the attention,
because of a possibility of using them in conjunction with scCO2 as media, for homogeneous
catalysis with catalyst recovery. Their task as a solvent in reactions and a catalyst is alike to
that provided by ionic liquids in biphasic catalysis. Nevertheless, liquid polymers are not as
polar as ionic liquids, they should be rather considered as a supplement to ionic liquids, not
a substitution.
To sum up, all polymers presented above have successfully proved to have the potential to
be extensively employed as media, for various reactions and catalysis [37].
Conclusion
An idea of green chemistry is aiming for replacement of commonly used solvent with
“green” ones, resulting in a reduced environmental impact. However, it leads to discussions
about supremacy of one green solvent over another. In the future scientists will have to focus
more on the solvent selection, basing on sustainable development and environmental
protection. To select properly, more data about new solvents chemo-physical properties and
their environmental impact is needed. Citing Elon Musk “We have no desire to do the best
green chemistry. We will do the best chemistry, and it will happen to be green”.
Literature
1. Jutz F., Adanson J.M., Balker A., Ionic Liquids and Dense Carbon Dioxide: A Beneficial
Biphasic System for Catalysis. Chem. Rev., 2011, 111 (2): 322–353
229
2. Sanni Babu N., Mutta Reddy S., Impact of solvents leading to environmental pollution.
National Seminar on Impact of Toxic Metals, Minerals and Solvents leading to
Environmental Pollution, Journal of Chemical and Pharmaceutical Sciences, 2014; ISSN:
0974-2115
3. Dick F.D., Solvent neurotoxicity. Occup. Environ Med., 2006; 63(3): 221-226
4. Malaguarnera G., Cataudella E., Giordano M., Nunnari G., Chisari G., Malaguarnera M.,
Toxic hepatitis in occupational exposure to solvents. World J Gastroenterol. 2012; 18(22):
2756–2766.
5. Lauwerys R., Bernard A., Viau c., Buchet J.P., Kidney disorders and hematotoxicity from
organic solvent exposure. Scand J Work Environ Health; 1985: 11(1): 83-90
6. Rama koteswararao P., Tulasi S.L., Pavani Y., Impact of solvents on environmentl
pollution. National Seminar on Impact of Toxic Metals, Minerals and Solvents leading to
Environmental Pollution. Journal of Chemical and Pharmaceutical Sciences, 2014; ISSN:
0974-2115
7. Welton T., Solvents and sustainable chemistry. Proc Math Phys Eng Sci., 2015;
471(2183): 20150502
8. Li C-J, Chan T-K. 1997. Organic reactions in aqueous media. New York, NY: Wiley.
9. Lindström U.M., Organic reactions in water: principles, strategies and
applications. Oxford, UK: Blackwell. ISBN: 978-1-4051-3890-1
10. Hyatt JA. 1984. Liquid and supercritical carbon dioxide as organic solvents. J. Org.
Chem. 49, 5097–5101
11. Beckman E.J., Supercritical and near-critical CO2 in green chemical synthesis and
processing. J. Supercrit. Fluids, 2004; 28: 121–191
12. Rayner C.M., The potential of carbon dioxide in synthetic organic chemistry. Org. Process
Res. Dev., 2007; 11: 121–132
13. Welton T., Room-temperature ionic liquids. Solvents for synthesis and catalysis. Chem.
Rev., 1999; 99: 2071–2084
14. Parvulescu V.I., Hardacre C., Catalysis in ionic liquids. Chem. Rev., 2007; 107: 2615–
2665
15. van Rantwijk F., Sheldon R.A., Biocatalysis in ionic liquids. Chem. Rev, 2007; 107:
2757–2785
16. Chandrasekhar S., Narsihmulu C., Sultana S.S., Reddy N.R., Poly(ethylene glycol) (PEG)
as a reusable solvent medium for organic synthesis. Application in the Heck reaction. Org.
Lett. 2002; 4: 4399–4401
230
17. Leininger N.F., Clontz R., Gainer J.L., Kirwan D.J., Polyethylene glycol-water and
polypropylene glycol-water solutions as benign reaction solvents. Chem. Eng. Commun.,
2003; 190: 431–444
18. Andrews P.C., Peatt A.C., Raston C.L., Indium metal mediated synthesis of homoallylic
amines in poly(propylene)glycol (PPG). Green Chem., 2004; 6: 119–122
19. Chen J., Spear S.K., Huddleston J.G., Rogers R.D., Polyethylene glycol and solutions of
polyethylene glycol as green reaction media. Green Chem, 2005; 7: 64–82
20. Clark J.H., Taverner S.J., Alternative solvents: shades of green. Org. Process Res. Dev.,
2007; 11: 149–155.
21. Blackmond D.G., Armstrong A., Coombe V., Wells A., Water in organocatalytic
processes: debunking the myths. Angew. Chem. Int. Ed., 2007; 46: 3798–3800.
22. Berkeley W.C., Zhang J., Green process chemistry in the pharmaceutical industry. Green
Chemistry Letters and Reviews, 2009; 2(4): 193-211
23. Li Ch.J., Trost B.M., Green chemistry for chemical synthesis. Proc Natl Acad Sci USA,
2008; 105(36):13197-13202
24. Song J., Han B., Green chemistry: a tool for the sustainable development of the chemical
industry. National Science Review, 2014; 2(3): 255-256
25. Szekely G., Jimenez-Solomon M.F., Marchetti P. , Kim J.F., Livingston A.G., Sustainability
assessment of organic solvent nanofiltration: from fabrication to application. Green Chem.,
2014; 16: 4440-4473
26. Sharma S.R., Green Chemistry, Green Solvents and Alternative Techniques in Organic
Synthesis. International Journal of Chemical and Physical Sciences,2015; 4 Special Issue-
NCSC-Jan-2015
27. Breslow R., The Principles of and Reasons for Using Water as a Solvent for Green
Chemistry. Part 5. Reactions in Water Published Online: 2010, Wiley-VCH Verlag
GmbH & Co. KGaA.
28. Chanda A., Fokin V.V., Oragnic synthesis “on water”. Chem Rev. 2009; 109(2): 725-748
29. Narayan S., Muldoon J., Finn M.G., Fokin V.V., Kolb, H. and Sharpless, K. Angew.
Chem. Int. Ed., 2005; 44(21): 3275.
30. Narayan S., Fokin, V. and Sharpless, K., Organic Reactions in Water, in (ed. M.
Lindstrom), Blackwell, Oxford, 2007; 350–365.
31. Breslow, R. and Maitra, U. On the origin of product selectivity in aqueous diels-alder
reactions. Tetrahedron Lett., 1984; 25: 1239–1240.
231
32. Branch J.A., Bartlett P.N., Electrochemistry in supercritical fluid. Philos Trans A Math
Eng Sci, 2015; 373(2057):20150007
33. Nalawade S.P., Picchioni F., Janssen L.P.B.M., Supercritical carbon dioxide as a green
solvent for processing polymer melts: Processing aspects and applications. Progress in
polymer science, 2006; 31(1):19-43
34. Patel D.D., Lee J.M., Applications of ionic liquids. Chem Rec., 2012; 12(3): 329-355
35. Keskin S., Kayrak-Talay D.,Ug ̆ur A., Hortacsu O., A review of ionic liquids towards
supercritical fluid applications. J. of Supercritical Fluids, 2007; 43: 150–180
36. Vekariya R.L., A review of ionic liquids: Applications toward catalytic organic
transformations. Journal of Molecular Liquids, 2017; 227: 44-60
37. Heldebrant D.J., Witt H.N., Walsh S.M., Ellis T., Rauscher J., Jessop P.G. Liquid
polymers as solvents for catalytic reductions. Green Chem. 2006; 8: 807–815
38. Verschueren K., Handbook of environmental data on organic chemicals, 4th edition,
Wiley, New York, 2001
39. Ulbricht J., Jordan R., Luxenhofer R., On the biodegradability of polyethylene glycol,
polypeptoids and poly(2-oxazoline)s. Biomaterials, 2014; 35(17):4848 -61
40. Feu K.S., de la Torre A.F., Silva S., de Moraes M.A.F., Corrêa A.G., Paixão
M.W. Polyethylene glycol (PEG) as a reusable solvent medium for an asymmetric
organocatalytic Michael addition. Application to the synthesis of bioactive
compounds. Green Chem., 2014; 16: 3169–3174
232