Luigi Vaccaro Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica, Università di Perugia Via Elce di Sotto, 8 – 06123 Perugia; Tel.

Luigi Vaccaro

Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica, Università di Perugia

Via Elce di Sotto, 8 – 06123 Perugia; Tel +39 075 5855541; Cell. +393384058969 [email protected]

http://www.chm.unipg.it/greensoc

A focus on GREEN CHEMISTRYNumber of publications where the term “Green Chemistry” appears

GREEN CHEMISTRY GREEN CHEMISTRY

PREVENTING POLLUTION SUSTAINING THE EARTH

Slide taken from the American Chemical Society

“ Chemistry has an important role to play in achieving a sustainable

civilization on earth.”

— Dr. Terry Collins, Professor of ChemistryCarnegie Mellon University

Slide taken from the American Chemical Society

WE SHOULD CONSIDER THIS QUESTION FROM

SEVERAL VIEWPOINTS:

The environment and human health.

A stable economy that uses energy and resources efficiently.

Social and political systems that lead to a just society.

Slide taken from the American Chemical Society

TO UNDERSTAND THE ROLE OF CHEMISTRY IN SUSTAINABILITY,

WE WILL LOOK AT THE FIRST TWO POINTS…

• The environment and human health.

• A stable economy that uses energy and resources efficiently.

Slide taken from the American Chemical Society

IN A SUSTAINABLE CIVILIZATION…

• Technologies used for production of needed goods are not harmful to the environment or to human health.

• Renewable resources (such as plant-based substances or solar energy) are used rather than those, like fossil fuels, that will eventually run out.

Slide taken from the American Chemical Society

IN A SUSTAINABLE CIVILIZATION…

• At the end of their use, materials are recycled if they are not biodegradable (easily broken down into harmless substances in the environment).

Slide taken from the American Chemical Society

BENEFITS OF CHEMICAL INDUSTRY:

• Antibiotics and other medicines• Fertilizers, pesticides• Plastics• Nylon, rayon, polyester, and

other synthetic materials• Gasoline and other fuels• Water purification• Organic Semiconductors

Slide taken from the American Chemical Society

WHILE WE HAVE MADE SOME PROGRESS IN ACHIEVING

THESE GOALS, WE STILL HAVE A LONG WAY TO GO…

• Mountains of solid waste are piling up—particularly in industrialized nations.

• Air and water pollution continue to be problems in many places.

Slide taken from the American Chemical Society

THE POLLUTION PREVENTION ACT OF 1990

This was the U.S. environmental law stating that the first choice for preventing pollution is to design industrial processes that do not lead to waste production.This is the Green Chemistry approach

“The Congress hereby declares it to be the national policy of the United States that pollution should be prevented or reduced at the source whenever feasible; pollution that cannot be prevented should be recycled in an environmentally safe manner, whenever feasible; pollution that cannot be prevented or recycled should be treated in an environmentally safe manner whenever feasible; and disposal or other release into the environment should be employed only as a last resort and should be conducted in an environmentally safe manner”

EPA – US Environmental Protection Agency

THE POLLUTION PREVENTION ACT OF 1990

US officially pointed the attention on the ‘‘millions of tons of pollution’’ and the related cost of ‘‘tens of billions of dollars per year’’ (Pollution Prevention Act 1990, p.617).

In US specific financial support is given through calls on Green Synthetic methodologies (SYN)

In Europe there are not specific actions for promoting academic/industrial efforts in this direction.

US EPA Presidential Green Chemistry Award

Promotes and recognizes green chemistry

Five Categories

1. Alternative synthetic pathways

2. Alternative reaction conditions

3. Design of safer chemicals

4. Small business

5. Academic investigator

Source: http://www.epa.gov/greenchemistry

“Alternative synthetic pathways Award”

1999 Lilly Research Laboratories (Talampanel)

2000 Roche Colorado Corp (Cymevene®)

2002 Pfizer, Inc (Zoloft®)

2004 Bristol-Meyers Squibb Company (Taxol)

2005 Merck & Co. Inc. (Emend®)

2006 Merck & Co. Inc. (Januvia®)

2006 Codexis, Inc. for Atorvastatin (Lipitor®)

2010 Merck & Co. Inc. and Codexis, Inc. (Januvia™ II generation)

Horizon 2020 The EU Framework Programme for Research and Innovation

where knowledge across different fields of organic chemistry are brought together to face the different issues that need to be settled in the route towards a sustainable development.

Excellence in Science; Industrial Leadership; Societal Challenges

Horizon 2020 and the research search for a sustainable future

2011 European Roadmap The European Association for Chemical and Molecular Sciences (EuCheMS) highlighted the importance of the strategic choices should be made for the European technological future.

The first European Sustainable Chemistry Award (Matthias Beller)

Green is the color of money …

The Chemical Manufacturers Association (CMA) launched the Responsible Care® program in 1988 to respond to public concerns about the manufacture and use of chemicals.

Part of the guiding principles of the Responsible Care® program is to make health, safety, the environment, and resource conservation critical considerations for all new and existing products and processes.

Currently, 52 nations by their national chemical industrial societies participate to this Program (Italy is included through Federchimica)…

Green is the color of money …

Green Chemistry is the common effort of Academia, Industry and Government to realize a Sustainable Civilization

- Save companies money by using less energy and fewer/safer chemicals, thus reducing the costs of pollution control and waste disposal.

-Train modern scientists and professionals who will contribute to a sustainable development of our Planet in the immediate future

- Create new and appealing job positions in industries that contribute to the wealth of the society

-Design more efficient processes that minimize the production of waste materials

- Use industrial processes that reduce or eliminate hazardous chemicals

- Make chemical products that do not harm either our health or the environment

GREEN CHEMISTRY …The rise of term Green Chemistry in US is related to a significant political and economic action devoted to save money and to promote innovative research

In Europe “Green Chemistry” is used with two other definitions that only partially overlap:

- “Clean Chemistry”: replace toxic substances and processes- “Sustainable Chemistry”: economic and industrial evaluation of a process in the current and future perspective

12 Principles of Green Chemistry

1. Prevent Waste

2. Design Safer Chemicals

3. Less Hazardous Chemical Synthesis

4. Use Renewable Feedstock

5. Catalysis

6. Avoid derivatives

7. Atom Economy

8. Safer Solvents

9. Energy Efficiency

10.Design Chemicals for Degradation

11. Real-Time Analysis for Pollution Prevention

12. Inherently Safer Chemistry for Accident Prevention

Design Safer Chemicals

• Water-based acrylic alkyd paints with low VOCs that can be made from recycled soda bottle plastic (PET), acrylics, and soybean oil. In 2010, Sherwin-Williams manufactured enough of these new paints to eliminate over 800,000 pounds of VOCs.

• Foam cushioning are conventionally manufactured from petroleum products. Cargill’s BiOH™ polyols are manufactured from renewable, biological sources such as vegetable oils. Each million pounds of BiOH™ polyols saves nearly 700,000 pounds of crude oil. Cargill’s process reduces total energy use by 23 percent and carbon dioxide emissions by 36 percent.

22H3C

O OCH3

O

Phenolic ethers, Pharmaceuticals, Flavours and Fragrances Quaternarium ammoniumcompounds

Surfactants, Softeners, Electronics

Diphenyl carbonateAromatic polycarbonates

Methylisocianate production

AllylcarbonatesOptical organic glasses

Aliphatic polycarbonate diolsPolyuretans

Oxoalcohol carbonatesSynthetic lubricants

Dialkyl CarbonatesGreen solvents

Paints, adhesives

Policarbonate 53 %

Coatings and paintings 28%

Agrochemicals 12%

Pharm. & Cosmetics 5%

Electrolite solv.2%

Design Safer Chemicals

Dimethyl Carbonate Tree and Its Industrial Uses

F. Aricò,M. Chiurato, J. Peltier and Pietro Tundo Eur. J. Org. Chem. 2012, 3223–3228

Use Renewable Feedstock

Biodiesel

Bioethanol

E.g. Mossi & Ghisolfi (M&G)

Safer solventsfor the chemical production

Water

Ionic Liquids

Supercritical Fluids (scCO2)

Solvent-free… best choice is NO SOLVENT

80-90%of waste in a chemical process is represent by the solvent used and mostrly dispersed in the environment

Green alternatives

Less Hazardous Chemical Synthesis

Invent novel chemical approaches by combining:

• Catalysis (better if heterogeneous)

• Safer solvents

• Multistep procedures

• Automated continuous-flow reactors

• Energy efficiency

Less Hazardous Chemical Synthesis

Classic batch approach produces ca 3000 Kg of waste each Kg of amino ketone

R1

O

R2

NH2

Synthesis of amino ketones

Automate flow approach using safer solvent produces only 2.3 Kg of waste each Kg of amino ketone

> 99.9% reductionAdv. Synth. Catal. 2012, 354, 908–916

Energy Efficiency

New materials to exploit renewable energies

Solar Energy Applications

Solar Energy Applications

Konarka’s solar cell

Power Plastic ®Power Plastic ®

portable portable

portable

flexible

flexible

flexible

Negishi coupling

R1 X R2XZn R1 R2+PdCl2(PPh3)2 /

2(i-Bu)2AlH

R1,R2= aryl, vinyl

Heck reaction

R1 XR2

R1

R2

Pd(OAc)2 ; K3PO4

DMF+

Suzuki-Miyaura reaction

R1 X R2B

HO

HO

R1 R2+Pd(PPh3)4; Na2CO3 AQ

Benzene-EtOH

Richard F. Heck Ei-ichi Negishi Akira Suzuki

Nobel Prize in Chemistry 2010 "for palladium-catalyzed cross couplings in organic synthesis“.

“[…] The challenge for chemists is to find new methods using widely available metal catalysts, or even metal-free alternatives to maintain access to key drugs and other products currently made using precious metals”.

Light from the Suncurrent approach is to convert petrol or the solar energy into

electric energy

Eff. = 3%

Eff. = 1%

Only 3 companies in the world are developing this technology using fibers prepared from petrol sources

Brighten your home, USA http://www.brightenyourhome.netHimawary, Japan http://www.himawari-net.co.jpParans, Sweden http://www.parans.com

ONE example of Italian creativity and excellence is pursuing the millennium challenge of preparing efficient lighting using fiber optics prepared from renewable resourcesHeadway Srl

Light from the Sunthe future is to take the Sun into our houses using fibers optic

Luigi Vaccaro

Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica, Università di Perugia

Via Elce di Sotto, 8 – 06123 Perugia; Tel +39 075 5855541; [email protected]

http://www.chm.unipg.it/greensoc