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“Laboratory experiments of organic synthesis and decomposition of hazardous environmental chemicals following green chemistry principles”
A. Valavanidis,Th.Vlachogianni and K. Fiotakis Department of Chemistry, University of Athens, University Campus Zografou, 15784 Athens, Greece E-mail: firstname.lastname@example.org, email@example.com, firstname.lastname@example.org
Abstract The basic principles of Green Chemistry cover a wide range of issues for Organic Synthesis of chemical compounds: design of organic synthesis processes to maximize prevention of waste, atom economy, the use of less hazardous chemicals and safer or environmentally benign solvents, renewable raw materials, energy efficiency and catalysis. Also, Green Chemistry is interested for the best form of waste disposal and design for degradation of chemical products after use, complying with pollution prevention measures and sustainable development. In the present paper we offer some important examples of Organic Synthesis with innovative “greener” techniques which can be used for teaching or/and applying in a chemical laboratory of a university. The “greener” organic synthesis of IBUPROFEN (active ingredient of many painkillers) is a typical example. The original synthetic route involved six consecutive steps and an overall atom efficiency of only 40%, while 60% of the mass of atoms ended up in waste products. The organic synthesis of Adipic acid (AA), a feedstock used to make nylon, using better oxidizing agents, a reaction without organic solvents and much less waste than the conventional route. The synthesis of Maleic Anhydride (MA), widely used in the manufacture of polyester resins and paints, is an example of replacement of dangerous starting chemical, the best selectivity and the “greener” synthetic route. Microwaveassisted organic reactions is another example that can apply to teaching laboratories, as well as ultrasound-assisted organic synthesis. Organic chlorinated chemical solvents are by far the most dangerous environmental pollutants because of the low biodegradability and their accumulation potential in soil, water and biological tissues. Chlorinated liquid wastes from organic is an important environmental issue. Various green methods have been used to decompose chlorinated solvent waste, using ultrasound to cleanup waste waters containing chlorinated organic compounds. This method has practical applications and can be used efficiently in the management of chemical liquid waste. These examples can be presented in laboratory classes for undergraduates and post graduates with the aim to promote and enhance the perception of Green Chemistry principles to students and scientists working in Organic Synthesis.
England. acetaminophen and ibuprofen.Introduction Organic Synthesis of chemical compounds. The old method starts from the compound 2-mehtylpropylbenzene that can be made from chemicals separated from crude oil. catalysis. so non-metallic catalysts must be developed (organocatalysts or enzymes) which perform useful catalytic functions. Οld and new “greener” synthesis of anti-inflammatory drug Ibuprofen Pharmaceutical drugs has become a booming business and their sales have more than quadruplet since 1985.9]. Finding also environmentally benign solvents is another important problem for chemistry experiments[5-7]. Panadol. The reactions involved in the synthesis of chemical products must minimize environmental impact and waste. Many solvents that are used at present in the chemical industry and in research laboratories are very flammable and toxic. One of the problem with the old synthetic method is that is a multi-step synthesis and produces overall a low yield. branded products: Aspro.3]. less waste. Energy efficiency is another filed that that new methodologies must take into account. Also. most of the toms of the reactants are incorporated in to the product. environmentally benign chemical techniques are growing in importance in academic and industrial research laboratories. In the 1990s the BHC Co developed a new greener industrial synthesis of Ibuprofen that had only three synthetic steps. The process has very good atom economy. Ibuprofen is also a member of non-steroidal antiinflammatory drugs. In this process. but finite natural resources will inevitable limit the ability to manufacture in wasteful ways. designed to maximize efficiency and reduce waste. 1960s. separation and purification of materials. atom economy and use of less hazardous chemicals in synthetic methods. The old catalysts were traditionally metals which are toxic and scarce. the use of safer. environmentally benign solvents. In recent years. In general the old organic synthesis of Ibuprofen had very poor atom economy. resulting in only small amounts of unwanted byproducts. design for degradation of chemical products after use and pollution prevention for sustainable development. renewable raw materials. Although every new chemical process is very difficult to satisfy all principles of Green Chemistry. The traditional industrial synthesis of Ibuprofen (Boots Co. resulting in large quantities of chemical byproducts which had to be disposed causing an acute problem of chemical waste and pollution. energy efficiency.increasing population . involving economical synthesis. protection of the health of workers and prevention of pollution . If reactions could be optimised to prevent the formation of by-products. Nurofen) was a six-step process. A very well known group of drugs are analgesics. a terminology used as one of the principles of Green Chemistry that must be improved. If each step has a yield of 90% then the second step will be 90X90 = 81%. The challenge for both academic and industrial laboratories is to devise sustainable strategies that meet the demand of chemical products from an ever. recent developments in green synthesis of organic compounds give the opportunity to introduce the new “thinking” in university teaching laboratories and laboratories in the chemical industry [2. In terms of atom economy the method is wasteful because in every step many of the atoms of the reactants used do not appear in the final 2 . such as aspirin. Large quantities are used in isolation. reducing the waste which has to be disposed [8. it must comply with some of them to be greener compared to older ones. then purification processes would be eliminated. The chemical industry has made great improvements in the efficiency of its processes. include prevention of waste. Green Chemistry promotes changes to attitudes among research chemists and managers of chemical industry to approach chemical processes in a more constructive way.
the industrial process of manufacturing Adipic acid involved oxidation of cyclohexanone or a cyclohexanone/cyclohexanol mixture with nitric acid. especially if we consider that 3.000 tones are made per year (only in the United Kingdom). which contributes to global warming and ozone depletion) as a by-product. But the most important was that reagents and products are the same in each step and only the catalyst differs. the overall figure is 40%.product. The new method was with the same starting material but in three steps. CO/Pd). In the last few years. such as Raney Nickel. Figure 1. Later. which inevitable produces NOx (nitrous oxide. which means that more than half the materials are wasted.6 and catechol which is used as a building block for pharmaceuticals and pesticides. with higher atom economy (77% yield) and less waste (using catalysts. In the past industrial synthesis of adipic acid used benzene as a starting material (non-renewable. Finally. efforts have been 3 . Old and new “greener” synthetic route for Iboprufen Experimental section Synthesis of Adipic Acid with an environmentally benign method Adipic acid is produced annually in excess of 2. The catalysts used in the green synthesis can be recovered and reused so that it generates no waste. The green synthesis of Ibuprofen (after the patent ran out in the mid-1980s) was able to be developed by alternative synthetic methodology. and every step has to start with fresh materials.000 million kilograms because it is used for the production of Nylon 6. which was the product of petroleum refining. In the old method the AlCl3 is not a “true” catalyst and has to be disposed in landfill sites. carcinogenic chemical).
The mixture is a milky white colour.2-cyclohexanediol with yields in the range of 45-86% . Heat the mixture gently. The case of Adipic acid has become in recent years the typical green chemistry synthesis in the organic teaching laboratory. under organic solvent. cyclohexanone and 1. After 45 minutes remove the flask and cool it for 3 minutes. using oxpoero tungsten and molybdenum complexes for the oxidation of cyclohexene. cyclohexanol. and can be added with a small Pasteur pipette. clean. With a pipette transfer 4 . i) Add in the following order: 0. such as Tungsten catalysts (Na2WO4 / KHSO4/ Aliquat 336 [11.12] Figure 2.5 mL) of 30% H2O2 (carefully. The first alternative method was the use of cyclohexene or cyclohexanone that can be oxidized directly to colourless crystalline adipic acid with aqueous 30% H2O2. Traditional route and “greener” synthetic route of Adipic acid New greener methods for the synthesis of adipic acid by oxidation with hydrogen peroxide have been developed ever since by various researchers.19 of potassium hydrogen sulfate (KHSO4). synthesis of adipic acid that is less damaging to the environment with the use of catalysts . In a dry 25 mL screw-capped round bottom flask add a special magnetic bar.25 g of sodium Tungstate dehydrate. B. v) mix the components by swirling the vial for 10 sec and add 1.accomplished in a greener. Adipic acid (AA) synthesis A.0 g of Cyclohexene.0 g (5. Also. The method is simple and can be applied to a teaching laboratory of organic synthesis .25 of Aliquat 336 (phase transfer catalyst) which is a viscous liquid. The scientist who developed this biocatalytic synthesis won the Presidential Green Chemistry Challenge Awards Program. ii) 0. causes burns in contact with skin). place in the flask on the Al block and start stirring the reaction mixture.coli).and halide-free conditions and the use of novel catalysts. C. Summer of 1998 Awards in the US [14-16]. scientists developed new biocatalytic synthesis of adipic acid from D-glucose which uses genetically engineered Klebsiella pneumoniae (a non-virulent strain of E. iv) 0. iii) 6. Slowly in the beginning for one minute and then more vigorously. Connect an air condenser.
et al.1-05% and V (0. 1998 ) C6H10 + 4 H2O2 →catalysts→ C6H10O4 + 4 H2O The new route does not produce hazardous chemicals yield of adipic acid is 90%. Stir and heat the mixture at 80-100 oC. place the beaker on ice. 281: 1646-1647. A.3 g of crude product). The synthesis of Adipic acid with the traditional and the new route can be considered also for atom (or mass) efficiency. Cool again. NO2. Leave the sample on the funnel for 5 min. Allow to cool 5-10 min. Recrystallization. Precipitation as white crystal. Isolate the crystalline product by filtration on a Büchner funnel. some stuck to the flask and stir bar) Cool the beaker on ice for 10 minutes. heat again.7% B. scratch the inside of the beaker with a glass rod. The yield of the reaction is 92-96%. C4H4O4). Product mass = (6C)(12) (10H)(1) (4 O)(16) (2N)(14) = 146 g Reactant mass = (6C)(12) (18H)(1) (8 O)(16) = 218 g Mass efficiency = 146/218 X 100 = 67% It is realized that mass efficiency is 11% higher than the traditional route. and the released N2O contributes to global warming and ozone depletion. AA starts to precipitate. Maleic 5 . E. Isolate the crude AA by filtration on a Büchner funnel. trying to avoid the Aliquat 336 catalyst (liquid layer on the top of the aqueous mixture. Rinse with cold water. Cool and determine its weight and melting point. N2O. Maleic Anhydrite synthesis under Green Chemistry principles Another very useful example of organic synthesis for teaching student on the advantages of green chemistry principles. New greener route from cyclohexene with hydrogen peroxide and the catalyst Na2WO4. A “green” route to adipic acid…. N2) In this method. The recrystallization with deionized water (1 mL for every 2. especially from the environmental and economic point of view. is the synthesis of Maleic Anhydride (MA) (cis-butenediol acid. rinse the beaker with 2 mL ice-cold water. Traditional Route from mixture of cyclohexano0ne/cyclohexanone with oxidation by nitric acid (in the presence of metals Cu (0. Transfer on a clean watch glass.02-0.the cloudy mixture to a smaller beaker.2H2O (1%) and [CH3(n-C8H17)3N] HSO4 (1%) (Sato. nitric oxide is hazardous. Add more water if acid do not dissolve. dry it in an oven (at 115 oC) for 10-15 min.”.1%) C6H12O + 2 HNO3 + H2O → C6H10O4 + NOx (NO. Product mass = (6C)(12) (10H)(1) (4O)(!6) = 146 g Reactant mass = (6C)(12) (18H)(1) (9O)(16) (2N)(14) = 262 g Mass efficiency = 146/262 X 100 = 55. Science.
5 O2 (air) →catalyst →C4H2O + 4H2O The reaction has a yield of 60% Product mass: (4)(12) (3)(16) (2)(1) = 98 Reactant mass: (4)(12) 3. started to generate MA as a by-product of the oxidation of naphthalene to phthalic acid and phthalic anhydride. fixed bed reactor C4H10 + 3. without the use of solvent was applied as a patent by the Standard Oil Company (Indiana) . This process is greener and more attractive.6%. All three routes of manufacture involved the feedstock of benzene. and is a valuable intermediate in the manufacture of 1. The industrial process got rid of toxic benzene and the atom efficiency of the synthesis was much better with minimum waste. butene or butane with air (oxidizing medium) passing over a Vanadium pentoxide catalyst at 3-5 bar pressure and temperature 350-450 oC. Overall. whereas the butane process produces only water as a by-product. But then in the 1970s the oil crisis brought changes to the manufacture of MA. (VO)2P2O5 catalyst .4% B. E. In terms of carbon efficiency the old route with 33% of the starting material and the formation of CO2 (global warming). Old process: Benzene feedstock . V2O5 and MoO3 catalysts. fixed bed reactor 2 C6H6 + 9O2 (air) → catalysts → 2 C4H2O3 + H2O + 4 CO2 The reactions has 95% yield Product mass: 2(4)(12) 2(3)(16) 2(2)(1) = 196 Reactant mass: 2(6)(12) 9(2)(16) 2(6)(1) = 444 Mass efficiency = 196/344 (X 100) = 196/444 (X100) = 44. the process change again. Delaware. Maleic Anhydrite Synthesis: Old and greener synthesis A. New process: Butane feedstock. Also.5(2)(16) (10)(1) = 170 Mass efficiency = 98/170 (X100) = 57. after ten years of research a new process was developed for n-butane oxidation to MA using a 6 . Two chemical manufacturers . USA). The butane process was adopted. Total world production of MA is in the range of one million tones annually Before the 1960s MA was a highly valuable chemical product with limited markets and little manufacturing competition. Manufacture process for the production of MA with the use of various catalysts (phosphorus-vanadium and phosphorus-vanadium-co-metal catalyst) at temperatures 0200 oC.Anhydride is widely used in the manufacture of polyester resins and paints. In the 1990s with the environmental concerns growing and with the emphasis on waste minimization. the butane feedstock provides the most “green” synthetic route .4-butanediol (used in polyurethane industrial process and in the preparation of butyrolactone (a solvent and paint remover).I du Pont de Nemours and Co (Wilmigton. UCB Chemicals and BASF.
high yielding and regioselective procedure by an intramolecular Friedel-Crafts alkylation in dry media of the corresponding 1-bromo-4arylbutanes immobilized in silica . Microwaveassisted reactions need much shorter times. decomposition of organic chemicals. An interesting example is the combined microwave and ultrasound assisted Williamson ether synthesis. simple. The chemical and physical effects of ultrasound arise from the cavitational collapse which produces extreme conditions locally and thus induce the reaction of chemical reactants which aRe not easily attained by conventional conditions. There are numerous examples of microwave-assisted organic reactions from a variety of scientific papers on the subject. Examples of ultrasound-assisted organic synthesis can be found in reviews [30. The process uses microwave irradiation to assist the free radical polymerization of monomers (MA and vinyl monomers) yielding high molecular mass polymers . Romania) scientists developed an alternative clean method for the synthesis of MA copolymers. Sonication enables the rapid dispersion of solids. (iii) (iv) Ultrasound-assisted organic synthesis: is Green Chemistry synthesis? The application of ultrasound as a method for organic synthesis has been recognized by organic synthetic chemists in the last decade. The scientific literature is full of novel organic syntheses of various chemicals by microwave-assisted reactions. (iii) An interesting microwave-assisted Diels-Alders reaction of anthracene with fumaric acid . The use of a synthetic method which is clean. Sonochemistry corresponds to the “green’ chemistry objectives: provides energy savings. no waste and high efficiency . Teaching laboratory exercises in Universities can be set up by using a commercial microwave oven. Microwave-assisted eco-friendly organic synthesis Organic reactions performed under microwave irradiation (MWT) have some significant advantages in comparison with conventional reactions at high temperatures. Some examples: (i) (ii) 2-alkylated hydroquinones under microwave irradiation using cyclohexadione and aldehydes catalysed by KF-Al2O3 in dry media  1. From the Institute of Macromolecular Chemistry (Iasi. have better selectivities and produce higher yields . efficient and economical without solvents and easier work-up for the products is inevitably environmentally benign procedure. which proves to be an efficient and ecologically valuable route for preparing ethers in the absence of organic auxiliary substances (such as phase-transfer catalysts) . 7 . A fast. and also can use aqueous media for non-classical reagents. high yields and selectivity in reactions.4- (ii) Fused polynuclear tetrahydro arenas with microwave irradiation. (iv) Various organic synthesis and the methodology of microwave-assisted irradiation can be found in numerous reviews [26-28].circulating fluidized bed reactor .31].
Bioremediation is another method which uses the metabolism of microorganism to break down chemicals as a source of food and energy.5% at 625oC in seconds.g. Experimental procedure. AOP methods are associated with the generation of hydroxyl radicals which a short-lived but potent oxidizing agent. Sonochemical degradation of chlorinated wastes in aerated solutions is another method. because of their persistence and bioaccumulation in aquatic organisms. it is expensive and produces toxic residue ash. In the presence of oxygen or air. In the last decades. An example of waste treatment of chlorinated waste in a chemical laboratory is the sonolysis of chlorobenzene in a Fenton (Fe2+ /H2O2) type aqueous system. A solution of chlorobenzene in water 1 mmol in 1L of distilled water was used.g. Fe/H2O2. for 60 minutes. Various techniques have been deployed for their disposal or treatment to become less hazardous to the environment. Electrochemical treatment has been proposed for the treatment of polychlorinated solvent waste because of several advantages Photochemical processes which are used for decomposition of chlorinated waste. Supercritical waster oxidation (SCWO) is another method which uses the water at high temperatures and pressures above its critical point. legislation is being provided for controlling the release of such pollutants in the environment and methods for their disposal are being developed which are very costly. Incineration is a widely employed technique for their destruction at high temperatures. The Advanced Oxidation Processes (AOP) by a combination of ultraviolet light (UV) and either oxidants (e.000 tones of chlorinated wastes (2/3 from Germany) were incinerated each year by an incinerator in the North Sea (Dutch sector) .3 mL/min and an injection volume of 10 μL . 100 mL of the solution was placed in a 150 mL conical flask. The flask was placed in a ultrasound bath operated at 2000 kHz with an input power of 200 W. The solution was bubbled for 2-3 mins with air and then closed. Chlorinated solvents are toxic substances. The various methods used for the treatment or destruction of chlorinate solvent waste are : Chemical dechlorination by various reagents (alkali metal polyethylene glycolate. H2O2. The temperature was 25 oC. TiO2 photocatalysis). The mobile phase was acetonitrile: water mixture (50:50). APEG) is an alternative method. but the method has also many disadvantages. Scientists are becoming aware of the importance of waste-minimisation schemes and methods for their safe decomposition to environmentally benign substances [33-35]. with a flow rate of 0. are used as solvents in many university laboratories for organic synthesis and inevitably there are large quantities of chlorinated solvents in any organic laboratory waste. The technique has been effectively applied to a range of chlorinated hydrocarbons. Sonochemical degradation is fast and the products are less hazardous to the aquatic environment . destruction efficiencies exceeding 99. The use of activated sludge process to remove polychlorinated substances from waste is another well established method. Also. Hydroxyl radicals are produced from water which give rise to advanced oxidative phenomena. The progress of the sonolysis can be monitored by HPLC every 10 minutes. especially in sites of contamination. 8 .Chlorinated aromatic waste in laboratories: disposal and decomposition Chlorinated hydrocarbons. The detection wavelength was 254 nm. the same method can be applied efficiently to a wide range of chlorinated organic compounds. In the 1980s around 90-100. Bioremediation can be made commercially viable by accelerating the work of natural bacteria residing at the site of contamination. In principle is an enzymatic biodegradation process. The degradation of highly chlorinated solvents is achieved by a combination of anaerobic and aerobic treatments. O3 ) or oxidants and a catalyst (e.
The examples of Ibuprofen. Degradation reaction products of chlorobenzene after sonication and possible reaction mechanisms. The replacement of toxic and noxious solvents by more environmentally-benign ones is an important area for the teaching the principles of Green Chemistry. Examples of the synthesis of AA and MA can be used in the laboratory exercises. and “greener” synthesis of organic compounds in order to teach new chemists the advantages but also the principles of Green Chemistry. 9 . atom economy and protection of the environment. carbon tetrachloride and chloroform has been phased out by industry and gradually from academic research laboratories. the degradation of chlorobenzene and other chlorinated solvents can be an interesting example for the recycling of dangerous to the environment chemicals. energy. Already. Results and Discussion Chemical laboratories for the teaching or Organic Synthesis in university and higher education establishments must introduce more efficient. Finally. Adipic acid and Maleic anhydride are very important to show the big changes happening in the last decades for the manufacture of basic chemical in industry and the benefits in terms of waste.Figure 3. Atom economy for various reactions can be calculated to give a picture of the efficiency of “greener” routes to organic synthesis. The use of microwave oven and ultrasound baths is another area that must be explored in chemical teaching laboratories. There are numerous examples to choose and many products can be prepared at short time and in clean form. benzene. new.
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