Archives of Medical and Pharmaceutical Sciences Research (AMPSR).2017,01(02):39-44.
Review Article
APPLICATIONS OF GREEN CHEMISTRY IN PHARMACEUTICAL CHEMISTRY AND DAY TODAY LIFE Rakesh K. Sindhu*1, Anuja Verma1, Divya Sharma, Saurabh Gupta, Sandeep Arora 1 Department of Pharmacognosy and Natural Products, Chitkara College of Pharmacy, Chitkara University, NH-64, Rajpura-140401, Patiala, Punjab, India
ABSTRACT Green chemistry is also known as sustainable chemistry. It is used to design of chemical products and procedures that reduce generation of hazardous chemical substances. Green chemistry applies diagonally the life cycle of a chemical product, including its manufacture, use, design, and ultimately disposal. Green chemistry is very helpful in prevention of pollution at the molecular level, it gives innovative scientific solutions, it reduces the negative impacts of chemical products on human and the environment health. Green chemistry's 12 principles (Prevent waste, Maximize atom economy, Design less hazardous chemical synthesis, Design safer chemicals and products, Use safer solvents and reaction conditions and Increase energy efficiency etc.). Green chemistry play important role in pharmaceutical in developing innovatory drug delivery methods which are less toxic and more useful, effective with minimum side effects and could help millions of patients. KEY WORDS: Green Chemistry, Pharmaceuticals, Hazardous chemicals, Pollution and Sustainable chemistry. INTRODUCTION A unique program was initiated by (EPA) the Environmental Protection Agency of US in 1991 to execute sustainable development in chemical technology and chemistry by industry, government and academia. There Poul T. Anastas used the word green chemistry [1-3]. Chemistry has indulge the beneficial things in the form of medicine, dyes, cosmetics, food products, nano particles, liquid crystal, polymers, paints, biomolecules, agrochemicals. Presently, various complex products can be manufactured easily. Nonetheless, chemical process not only yields the required product but also the unwanted or undesired and harmful substance in large quantities in the form of liquid, gases, and solid. This has become the massive threat for the chemistry. So for the synthetic chemists the reduction of the chemical pollution has become the critical urgency [4-12]. Sustainability and Green chemistry go in one breath. Sustainable development is a process of reaching the requirements of the present era without negotiating the proficiency of unborn age group to complete their own needs. The concepts of Green chemistry are not new or unused rather it is new approach towards the sustainability. Mishaps occur basically due to the chemical/physical properties of the molecules we analyze. By the designing of the drug at molecular level, and type of reaction conditions and the reaction we select, we can also deal with vital problems like renewability, toxicity, and global impact [13-16]. Due to these logics, Green Chemistry is an advanced chemical philosophy. Its concepts inspire the designing of innovative processes and raw materials that minimizes the utilization of harmful substance and their production. Green chemistry’s concepts stands for two most important components:-
Correspondence Author* Rakesh K Sindhu Department of Pharmacognosy and Natural Products, Chitkara College of Pharmacy, Chitkara University, NH-64, Rajpura-140401, Patiala, Punjab, India
[email protected] Article info: Received Date: 27.05.2017 Revised Date: 25.07.2017 Accepted Date: 16.09.2017
1. First, Green chemistry depicts the dilemma of efficient usage of starting materials for synthesis and the associated reduction of waste due to their use. 2. Second, it accords with the safety, environmental issues and health which are correlated with the manufacturing, usage of chemicals and their disposals. The people which are practicing chemistry in the industry, research, and education to them the transformations in the Green chemistry provides an ample number of challenges. With these challenges yet, there are almost comparable freedom to light upon and use advanced chemistry in day to day life, for the improvement of economics of chemical manufacturing and to upgrade the better image of chemistry. Green chemistry is proved to be an advance section of chemistry which is obtained from the needs to reduce the injurious effect of chemicals and to minimize the amount of environmental pollution obtain from harmful chemicals [16]. Green chemistry provides a new approach [13-16] to the synthesis, processing and application of chemical substances in such a manner as to reduce threats to health and the environment. This new approach is also known as: • Environmentally benign chemistry • Clean chemistry • Atom economy • Benign-by-design chemistry The guiding principle is the design of environmentally benign products and processes was first pointed by Poul T. Anastas [1-4]. The concept is manifested in following twelve principles of green chemistry:1. Waste prevention instead of remediation 2. Less hazardous chemicals 3. Atom Efficiency
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Archives of Medical and Pharmaceutical Sciences Research (AMPSR).2017,01(02):39-44. 4. Safer products by design 5. Energy efficient by design 6. Innocuous solvents and auxiliaries 7. Preferably renewable raw materials 8. Shorter syntheses [avoid derivatization] 9. Inherently safer processes 10. Design products for degradation 11. Analytical methodologies for pollution prevention 12. Catalytic rather than stoichiometric reagents HISTORY DEVELOPMENT Green chemistry was founded very earlier. It can be linked to trembled activities of environment like Rachel Carlson. She published “Silent Spring,” in 1962 which was directly helpful to the public’s awareness related to pesticides and also their ties to environmental pollution. After some time of this publication, The EPA was established in 1970.The EPA shows it presence as the extended shadow of Rachel Carlson who is acknowledged as a foremost pioneer of environmental protection, a reason that has paved the way to current green chemistry practices. After a decade, act for the prevention of pollution was employed in 1990. This act was helpful for the reduction of pollution in an innovative way and this made the path for green chemistry [17]. Paul Anastas along with John Warner framed word “green chemistry” and on behalf of that they originated the twelve principles of green chemistry. Then Ryoji Noyori selected three points for developments in green chemistry, in 2005: 1. Employ green solvent like supercritical CO2 (carbondioxide), 2. For clean oxidations the use of aq.hydrogen peroxide and 3. The application of hydrogen in asymmetric production. There has been a deviation in the evolution of green chemistry trends due to the links of previous decades. By the eco-awareness among consumers in market and the better information about the hazards of several materials and chemicals, various companies and manufacturers are working to restore the way for the manufacturing of their products by using chemicals. These may comprise: • Reduction of formaldehyde [cancer causing gas] which is used in the manufacturing of goods. • Less application of dyes in product synthesis. • Eliminating CFC’s producing products as they depletes the ozone layer. • New advancements in technologies through chemicals that decreases the green impact or conversion to low-carbon chemicals. • Employing a patented organisation to obtain and phase out untreated materials for manufacturing. • For the agrochemical farming treatment developing sustainable technology PRINCIPLES OF GREEN CHEMISTRY Basically, Green Chemistry objective to reduce threats at the design stage. It is beneficial for our health and the environment to eliminate hazardous practices from the chemical design process starting [18]. It will be then helpful all the way through the design, production, use or reuse and dumping processes. Following Twelve Principles of Green Chemistry are shown with suitable examples [19]. 1. The utilization of techniques which makes the less solvent use – Prevention [20]. 2. use of catalyst for the hydrogenation of carboxylic acid to aldehyde – Atom economy [21]. 3. Oxidation of cyclohexane oxidation by the application of hydrogen peroxide adipic acid is synthesised- Less Hazardous Chemical Synthesis [22]. 4. Less dangerous pesticides use - Designing Safer Chemicals [e.g. Spinosad] [23]. 5. Supercritical fluid extraction - Safer Solvents and Auxiliaries [24].
6. Alternative for PWC, Polyolefins-polimer - Design for Energy Efficiency [polymerization taking place with lower energy consumption] [25]. 7. Manufacturing of surfactants - Use of Renewable Feedstock [26]. 8. In the preparation of sample, the on-fibre derivatization against dervatization in solution is done - Reduce Derivative [27]. 9. Synthesis of b-enaminones from 1,3-dicarbonyl compounds and amines in presence of Efficient Au [III] as a catalyst - Catalysis [28]. 10. Manufacturing of biodegradable polymers - Design for Degradation [29]. 11. For wastewater monitoring in-line analysers used - Real-time analysis for Pollution Prevention: 12. Di-Me carbonate [DMC] ,an environmentally affable alternative for Di-Me sulphate and Me halides in methylation reactions Inherently Safer Chemistry for Accident Prevention [30]. APPLICATIONS OF GREEN CHEMISTRY 1. Chemicals from glucose: These are the chemical compounds are a set of chemicals which might be made on a completely massive scale to satisfy international markets. Glucose is alternative for product chemicals. Biotechnological strategies are used to control the production of fragrant compounds], compounds inclusive of catechol, hydroquinone, and adipic acid, every compounds of which be able to be vital, may be synthetic. Benzene is the initial material used for these materials, by means of changing benzene amid glucose can assist in lowering the usage of diverse reagents with certain toxic. Synthesis which takes region in water as a replacement for of natural solvents is more beneficial [31]. 2. Polysaccharide Polymers: They are an essential group of compounds that include widespread packages. they have got their dangerous consequences. The big range of compounds can be exploited. Polysaccharide because the feedstock have to be used as beginning materials due to the fact that it's far extra environmentally feedstock. Those are organic and have the benefit of being renewable or viable, in place of petroleum feedstock. On the opposite side these don't have any chronic toxicity to environment and health of humans. A few more reactions are: a) Green chemical reactions: • Production of aromatic amines which are halide free: Conventional manufacturing of aromatic amines is done by treating benzene with chlorinewith the help of nitrogen and then displacing chlorine with a brand new group (nucleophilic substitution). In this process nitrobenzene together with aniline is heated in the presence of tetramethyl ammonium hydroxides to formtetramethyl-ammonium salts . The technique avoids using halogenations intermediates. • Homogeneous catalysis and atom economic system: This system was advanced by Trost. The objective of this work is to reduce the useless by products of atoms formed during process.[31]. b) As green reagents: • Liquid oxidation reactor: It allows safe oxidation of organic chemicals with pureoxygen.It can cause reaction to occur at low temperature and is quite useful. Due to this the amount of vent gas has been decreased. • Complexes formed by green oxidative transmissions: various oxidation methods have bad ecological impacts. The contaminate (metal ion) can be decreased by the use of molecular oxygen as the number one oxidant. Many ligands have been advanced that are strong towards oxidative decomposition in oxidizing environments. because of this it's miles viable to synthesize stable excessive oxidation kingdom transition metal complexes. • Non phosgene isocynate synthesis: polyurethanes are the maximum crucial polymers. Polyurethanes are typically prepared by using phosgene. However phosgenehas disadvantage of being exceedingly poisonous gasoline. Its acute give up factor is lethality. To keep away from the poisonous gas phosgene, a technique is used where precursors of poly-urethanes and their isocyanate are synthesized. c) Reaction conditions for green solvents: 40
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Archives of Medical and Pharmaceutical Sciences Research (AMPSR).2017,01(02):39-44. • Making solvents immobile: For solvents which have high quantity and vast applicability, the capacity for their poor impact on human health and the environment may be very high. Various solvents are comfortable and hard to handle [32]. d) Manufacturing drugs: Drugs which are oligonucleotide: Artificial oligonucleotides drugs are increasing class of drug molecules with wide range of healing property. Presently, production is done by making use of HL-30™, (a polystyrene bead) at a dose of 90 mmol/g. It has numerous limiting characteristics: [i] Non-biodegradable [ii] non-renewable[ iii] it contributes ~40% of raw materials fees [iv] It is a single-supply raw material e) Products of green chemicals: • Other methods for designing nitrites: Different structures of compound that can be toxic are studied and changes are done to reduce toxicity. The mechanism causing acute toxicity is thought to be due to removal of hydrogen cyanide from cyanohydrins, depending on the nature of the substitution at alpha carbon function may be decreased or improved. • Polyaspartic acids(donlar’s): By means of the usage of bio rational techniques the soybean cyst nematode can be managed: Soybean cyst nematode fungus is still a agricultural hassle. Being part of an inter disciplinary attempt to find a bio rational solution to the problem, various glycinoeclepinA analogues(a natural hatching stimulus of the nematode) have been developed and testing done. Number of the analogues were found to have inhibitory action on the hatching of soybean cyst nematode eggs. These eggs in the woman can last for eleven to twelve days in soil [33]. GREEN CHEMISTRY IN ROUTINE LIFE 1.Green Dry Cleaning of Clothes: Per-chloroethylene is most common solvent used for dry maintenance. It is also suspected as a cause of cancer. Micell technology [34], uses liquid CO2 and a surfactant for dry cleaning clothes, in the place of PERC and CO2 so that need of halogenated solvent get eliminated [35]. 2. Bleaching Agents: The paper is produced from wood. The wood may consist of approximately seventy percent polysaccharides and about thirty percent lignin. The amount of lignin must be removed from the wood to get a good quality paper. For thr removal of lignin various reagents used like, sodium hydroxide, sodium sulphide and chlorine gas. But on the other hand it is also causing environmental pollution and various other problems. For the decomposition of lignin the reaction with Chlorine also result in many other hazardous products. Dioxins and furans are produced like chlorinated furans and 2,3,4tetrachloropdioxin. They are by products of chemical reaction of Chlorine and aromatic rings of the lignin. These products cause different health problems and cancer. Latter on, chlorine gas was replaced by chlorine dioxide. There are other agents like O3, H2O2 or O2also did not give this the desired products. Terrence Collins of Camegie Mellon University has developed a versatile agent. In this, use of hydrogen peroxide as bleaching agent takes place in the presence of different activators known as TAMLs [Tetra Aamido Macrocyclic Ligands] activators [36]. The catalytic action of TAMLs activators grants H2O2 to break down more lignin at low temperature in less time [37]. 3. To Change Turbid Water into Clear Green Solution: In present era the use of alum salt to treat municipal and industrial waste water clear is in practice. It has been raised that alum is not perfect for this purpose because it increasing the hazardous ions in discharged water and may cause Alzheimer’s ailments. Therefore, agriculture waste that discharged such as kernel powder and taramind seeds, acts as an efficient agent to compose municipal and industrial waste water clears [38]. Powder of Kernel is harmless. It is also ecofriendly and cheaper than alum. Four different flocculants taken for the testing, that is kernel powder, seeds of tamarinds, mixture of the starch and alum, and powder and starch mixture.
Slurries prepared by the addition of weighed amount of clay, sand and water to the given flocculants. [39]. FUTURE TRENDS IN GREEN CHEMISTRY: Chemists are using their innovative and creative skills from all over the world to build up new processes, reaction conditions, synthetic methods, catalysts etc. Profitable applications of green chemistry have led to intellectual research to find out different alternatives to the active artificial methods and some environmental laws [40-48]: These laws are in general have become "command and control" laws. Risk occurring with toxic chemical is a function of Hazard and Exposure. With the passage of time, these laws have completed a great deal in improving pollution prevention in coming years [49]. TEACHING OF GREEN CHEMISTRY Here is one main question, the way to educate the new coming back age group of chemists holding, information along with ample of talent to apply eco-friendly chemistry slander within the hub of academic resources that are associated with green chemistry [50]. Education is incredibly necessary within the favour of green chemistry. It is skilful for each at the extent of world and on the extent of pro-environmental education. In today’s era chemists square measure accustomed to new ways of chemical compound syntheses instead of ancient ways. The inexperienced chemistry includes the information associated with property by coming up with and mistreatment the ways during which natural organic materials are tight handled. Green chemistry additionally includes data concerning introduction of safety merchandise for man, reduction of unsafe volatilized, liquid and solid wastes and therefore the intellectual usage of energy sources. The promotion of inexperienced chemistry among the staff in chemical industrial plants, in faculties and distributors of chemical merchandise plays important role. The large information of inexperienced chemistry deeds can change US to balance economy, atmosphere and therefore development of environment is profitable for society. The various educational resources are presently available in market and also on Internet. They are proved be useful in the process of everyday teaching related to green chemistry principles, [51] e.g. 1. Green Chemistry Resources, ACS ,homepage:www.acs.org/education/greenchem. 2. Green Chemistry Institute: chemistry.org/green chemistry institute. 3. EPA Green Chemistry Program: www.epa.gov/greenchemistry. 4. Green Chemistry, journal of the Royal Society of Chemistry: www.rsc.org/is/journals/current/green/greenpub.html. PHARMACEUTICAL APPLICATIONS Pharmaceutical companies have the capacity to improve the environmental performance by using the knowledge related to green chemistry [52]. Green chemistry is engaged in developing innovative drug deliverance methods which are less toxic and more useful, efficient and could help millions of patients [53], Examples :1. Phosphoramidite: solid-phase which is blend of antisense oligonucleotides has been altered to entrain the concepts of green chemistry by discarding the usage and formation of toxic or hazardous materials and recycling the important materials like protecting groups amidites and solid support, thus upgrading the cost-efficiency and atom economy [54]. 2. The formation of Naproxen with chiral metal catalyst containing 2,2'-bis[diphenylphosphino]-1,1'-binaphthyl ligand with fine quantity of product and this was described by Anastas et al [55]. 3. The green chemistry used in the manufacturing of a key intermediate of atorvastatin and the processes take place in two steps :a) In first step, bio catalytic reduction of Ethyl-4-chloro-3oxobutanoate occurs with combination of keto-reductase and glucose for regeneration of the useful substance which is essential for activity of enzyme forming a product [S]ethyl-4-chloro-3hydroxybutyrate with high yield. b) In next step, a halohydrinde halogenase is used to accelerate the substitution of the chloro with cyano group, and this reaction takes 41
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Archives of Medical and Pharmaceutical Sciences Research (AMPSR).2017,01(02):39-44. place at neutral pH and atmospheric temperatures in presence of natural catalyst.[56]. c) Few workers have invented clean, quick and inexpensive way for the preparation of amines with huge portion of drug molecules. presently, industries manufacture amines in a two-step process at high cost and it results in grand amounts of by-products as a waste material [57]. On the other hand, concepts of Green chemistry don’t produce any waste product, and reaction is also a quick onestep process in presence of little amount of catalyst. Steps for Aspirin synthesis with microwave irradiation using catalysts such as H2SO4, MgBr3.OEt2, AlCl3, CaCO3, NaOAc, Et3N and solventfree approach have been designed [58]. Case studies (green processes used in pharmaceutical development) 1. Quinapril:Quinapril hydrochloride is used for the cure of hypertension and CHF. It acts as an ACE (angiotensin converting enzyme) inhibitor [59]. Methylene chloride used is a potentiallyviolent hydroxy-benzotriazole,dicyclohexylcarbodiimide [DCC] used as sensitizer, and sufficient amount of toluene volumes is used for separating acetic acid from the mixture by the process called solvent exchange method, uses the variety of undesirable routes for the original manufacturing. By Berkeley et al. 2009, method. The main focus is on eliminating use of acetic acid, which would allowed to reduce the diketopiperazine formation. the overall yield rises from 58 to 90%. The production of toxic material has been reduced significantly and less chemicals and greener solvents have been used.[60] 2. Celecoxib: It is a widely used as a cyclooxyginase -2 antiinflammatory agents. It is moderately simple and possess a sensible synthetic process until it reaches the developmental stage [61, 62]. There has been increase in the yield from 63 to 84%, decrease in the productionof waste by 35% and minimize the usage of the harmful hydrazine. Due to the change in conditions of reaction it is proved that product isolation needs only cooling upto 208ºC in place of 58ºC. At last, there is a change in cake wash solvent from 100% isopropanol to 50% aqueous isopropanol due to cleaner product. The process completely abolishes the use of undesirable and unwanted solvents like methylene chloride and hexane, and eliminated the need for 5200 metric tons of solvent annually when combined with other changes.[60]. 3.Sildenafil citrate: It is first drug which was effectively used for oral treatment for erectile dysfunction.The route was first developed at Pfizer’s UK laboratories which includes a straight eleven steps for synthesis, and gave a 4.2% total production from 2-pentanone. The redesigned chemistry process proved to be beneficial for sildenafil citrate, as it increased the yield significantly. This process improved production, decreased the wastage of green solvents likeethyl acetate, water and t-butanol. According to the development process ethyl acetate could be used over three regular steps i.e. a] Addition of hydrogen, b] Activation by acid, c] Acylation, which made the process easy, simple and eliminated the requirement of totally exchange solvents among entire steps, and also made it a most important energy saving and waste elimination solvent method [60, 63-66]. 4. Amino acid derivatives for hepatoprotection Synthesis of a series of different amino acid-having thieno [2,3-d] pyrimidine group was done through green chemistryby incorporating water (as a solvent) to produce 2a-f, which were further acidified to acheive the targeted compound 3-9. In addition, synthesis of a tricyclic imidazothienopyrimidine was done. The characterization of starting compounds was done by microanalysis, FT-IR, Mass and 13C1 HNMR spectroscopy. The amino acid-derivatives that were obtained were screened for post-irradiation protection efficacy in young rats. Oxidative stress was induced using γ-Irradiation. However, most newly synthesized derivatives displayed prominent protective effects against injuries produced by γ-irradiation, by enhancingthe activity of different biochemical parameters in blood and altering the hematopoietic system. These results showed that anti-inflammatory and antioxidant mechanism of these compounds
could be due to the down-regulation of NF-κB protein expression in liver(hepatic) tissues. Hence, NF-κB could regulateIL-6 levels and TNF-α,CYP2E1 gene expression and COX-2 effects. The most active moiety was found to be Methionine derivative 8 [67]. 5. Metal organic frameworks cause the adsorptive elimination and partition of chemicals Elimination of harmful chemicals and their separation from the environment has become a vital issue. At present, adsorptive elimination is important for maintainence. Therefore, adsorption and removal of various nitrogen containing compounds, olefins, sulphur compounds and π-electron-rich gases via π-complex formation between an adsorbent and adsorbate molecules is very competitive. Porous metal-organic frameworks are much efficient in the adsorption or separation of different liquids and gases without harming their distinct characteristics [68]. 6. human bone replacement with Coral skeletons Coral skeletons can regenerate replacement human bone in nonloadbearing excavated skeletal locations. A combination of multiscale, interconnected pores and channels and highly bioactive surface chemistry has established corals as an important alternative to using healthy host bone replacements. Coral skeletal systems are being remolded into new calcified structures or synthetic corals by biomimetic processes, as places for the organized permeation of bone tissue cells and blood vessels. Progressive technologies in coral aquaculture and self-organization inorganic chemistry are helping to modify natural corals and create synthetic coral architectures able to accelerate bone regeneration with proper host integration at more skeletal locations, adapted to recent surgical techniques and used to treat intrinsic skeletal deformities and metabolic conditions [69]. 7. Synthesis of carotenoids from natural sources The synthesis of Atisane-type diterpenoids are the principal constituent of tetracyclic C20 -diterpenoids, widely isolated from the plant kingdom with varying degrees of structural complexity and pharmacological activity. Divergent total synthesis is an effective tactic to synthesize several atisane-type diterpenoids using structural interconversion from a common intermediate. They are also very helpful in synthesis of carotenoids[70]. 8. Extraction of Carotenoids from Microalgae and Seaweeds The production of carotenoids from algal sources at large scale made it most famous topic of interest for industries (health, cosmetic and nutrition applications) and also for commercial level. Marine microlage and seaweeds are the sustainable source of several biologically active substances. They are source for various natural carotenoids including β-carotene, zeaxanthin, violaxanthin, lutein, astaxanthin and fucoxanthin. Conventional processing techniques serve simple procedure to isolate carotenoids. They suffer some, innate limits including low efficiency, consumption of solvent in large amount, its selectivity and time for long treatment, leading to new advancements in the search for inventive extraction technologies like green chemistry[71]. CONCLUSION: Chemistry has invented many beneficial things from drugs and it not only yields the required product but also the other harmful and undesirable waste. This became a great challenge for the environmental sustainability which requires more efficient technologies to get rid off from these mishaps. It is the challenge for the prospect industries is to synthesise non-harmful products. Green chemistry provides a big platform to overcome from these unwanted harmful substances. It opens a multifaceted and wide research scope for the invention of more efficient reaction process to minimize the waste and maximize the desired product yield. But green chemistry alone cannot reduce these impacts. It requires twelve principles of green chemistry, given by Poul T. Anastas and J.C. Warner. They help to pave a way towards the greener world. By using the proper sample preparations one can obtain accurate and exact results of analysis. Enormous efforts are still undertaken for the designing of an superlative process which initiated with pollution free raw material and obtaining no secondary product and does not require any solvents for purification, isolation and chemical conversion. It is 42
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Archives of Medical and Pharmaceutical Sciences Research (AMPSR).2017,01(02):39-44. exceptionally essential to make the green chemistry concepts clear among students for better outcomes. CONFLICTS OF INTERESTS Declared none. REFERENCES 1. Anastas PT, Warner JC. Green Chem Theory and Practice. Oxford Univ. Press, New York 1998. 2. Anastas PT, Horvath IT. Innovations and Green Chemistry. Chem. Rev. 1997, 107, 2169. 3. Anastas PT, Williamson TC [Eds.]. Green Chemistry: Frontiers in Chemical Synthesis and Processes. Oxford University Press, Oxford 1998. 4. Anastas PT, Kirchhoff MM. Acc. Chem. Res. 2002, 35: 686-693. 5. Anastas PT, Heine LG, Williamson TC [Eds.]. Green Chemical Syntheses and Processes. American Chemical Society.Washington DC. 2000. 6. Anastas PT, Farris CA [Eds.]. Benign by Design: Alternative Synthetic Design for Pollution Prevention. ACS Symp. Ser.nr. 577, American Chemical Society, Washington DC, 1994. 7. Clark JH, Macquarrie DJ. Handbook of Green Chemistry and Technology. Blackwell, Abingdon 2002. 8. Matlack AS. Introduction to Green Chemistry. Marcel Dekker, New York 2001. 9. Lancaster M. Green Chemistry: An Introductory Text, Royal Society of Chemistry, Cambridge. 2002. 10. Clark JH [Ed.]. The Chemistry of Waste Minimization. Blackie, London 1995. 11. Ravichandran S, IntJ. ChemTech Res. 2010, 2:2191. 12. Trost BM. Atom economy—A challenge for organic synthesis: Homogeneous catalysis leads the way. Angew Chem Int Ed. 1995. 34: 259. 13. Sheldon RA. Green solvents for sustainable organic synthesis: State of the art. Green Chem. 2005, 7, 267. 14. Clark JH, Luque R, Matharu AS. Green Chemistry, Biofuels, and Biorefinery". Annual Review of Chemical and Biomolecular Engineering. 2012, 3:183–207. 15. Ahluwalia VK and Kidwai M. New Trends in Green Chemistry. Anamaya Publishers, New Delhi, 2004. 16. Anastas PT, Horvath I, IT Innovations and Green Chemistry, Chem.Rev.2007, 107:2169. 17. Anastas PT and Warner JC, Green Chemistry: Theory and Practice. Oxford Science Publications, Oxford. 1998. 18. Poliakoff Martyn, Fitzpatrick J Michael, Trevor Farren Paul I, Anastas. Sci. 2002, 2, 297. 19. See Resources section plus visit http://www.epa.gov/ green chemistry/index.html. 20.Anastas PT, Warner JC. Green Chemistry Theory and Practice; Oxford University Press: New York 1998. [b] Woodhouse EJ. Chemical States; Casper, M.Ed.; Routledge: New York 2003. [c]Tucker JL. Org. Process Res. Dev. 2006, 10,315. 21. Namieoenik J, Wardencki W. Solventless sample preparation techniques in environmental analysis. J High Resol Chromatogr. 2000, 23, 297. 22. Sato K, Aoki M, Noyori R. A Green Route to Adipic Acid: Direct Oxidation of Cyclohexenes with 30 percent hydrogen peroxide. Science. 1998, 281:1646. 23. Woodhouse EJ and Breyman, S. Green chemistry as social movement?". Science, Technology, & Human Values. 2005, 30:99–222. 24. Bardley D, Dyson P, Welton T. Room temperature ionic liquids. Chem. Rev. 2000,9: 18. 25. Romano U, Garbassi F. The environmental issue. A challenge for new generation polyolefins. Pure Appl.Chem. 2000,72:1383. 26. Nicolas N, Benvegnu T, Plusquellec D. Surfactants from renewable resources. Actualite Chimique 2002, 7-:11-12. 27. Stashenko EE, Puertas AM, Salgar W, Delgado W, Martinez JR. Solid-phase microextraction with on fibre derivatization applied to
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