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• Sustainable Materials • Academic-Industry Collaborations • Chemicals Policy • Cosmetics • And More!
Early Bird Registration will be open from February 15 until April 28, 2017
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Upcoming ACS Webinars www.acs.org/acswebinars Thursday, February 23, 2017
Fighting Cancer: Epigenetic Targets for Oncology Session 2 of the 2017 Drug Design and Delivery Symposium
Stuart Conway, Professor of Organic Chemistry, University of Oxford Sharan Bagal, Senior Medicinal Chemist, AstraZeneca
Thursday, March 2, 2017
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“Natural, Sustainable Innovation: L’Oréal’s Commitment to Renewable Materials and Eco-Friendly Processes”
David Constable Science Director, Green Chemistry Institute, The American Chemical Society
Xavier Marat Group Leader, Advanced Research, L’Oréal
Michel Philippe L’Oréal Fellow, L’Oréal
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2/16/2017
NATURAL, SUSTAINABLE INNOVATION: L’ORÉAL’S COMMITMENT TO RENEWABLE MATERIALS & ECO-FRIENDLY PROCESSES Michel PHILIPPE, PhD and Xavier MARAT, PhD - L’Oréal R&I
1st WORLDWIDE COSMETIC GROUP
205 25.8 140 82,900 32
Products sold every second Billions € (2016)
countries
people International brands
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2/16/2017
ALL THE BEAUTY NEEDS
Make up
Hair care
Perfume
Skincare
Hair dye
17
Audience Survey Question ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT
About how many patents does L'Oreal hold? • Almost 250 patents • Almost 300 patents • Almost 425 patents • Almost 500 patents
• Almost 750 patents
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2/16/2017
RESEARCH & INNOVATION 761 748 680 523
539
2008
2009
582
2010
624
2011
2012
2013
794M € (2015)
2014
3,870
497
people
patents
19
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2/16/2017
I N N OVAT I N G SUSTAINABLY
DEVELOPPING SUSTAINABLY
PRODUCING SUSTAINABLY
LIVING SUSTAINABLY
21
INNOVATING SUSTAINABLY BY 2020, WE WILL INNOVATE SO THAT 100% OF OUR PRODUCTS HAVE AN ENVIRONMENTAL OR SOCIAL BENEFIT.
22
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INNOVATING SUSTAINABLY • the new formula REDUCES THE ENVIRONMENTAL FOOTPRINT • the new formula uses RENEWABLE RAW MATERIALS SUSTAINABLY SOURCED or raw materials derived from GREEN CHEMISTRY • the new packaging has an IMPROVED environmental profile • the new product has an ENVIRONMENTAL or SOCIAL POSITIVE IMPACT
23
ECO-DESIGN APPROACH
24
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2/16/2017
L'Oréal has implemented Green Chemistry Principles for Many Years
http://youtu.be/QOi3ja1TaDo
L’Oréal commitment to Green Chemistry
25
COMMITMENT TO GREEN & SUSTAINABLE TRANSFORMATIONS Safe by Design to ensure maximum human and environmental health / safety To develop innovation
From our internal Chemistry
And from Suppliers
Following the basic GREEN CHEMISTRY principles, published by P. T. Anastas and J.C. Warner
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COMMITMENT TO GREEN & SUSTAINABLE TRANSFORMATIONS 12 PRINCIPLES OF GREEN CHEMISTRY
(Anastas P., Warner J.C., Green Chemistry, Oxford University Press, New York, 1998, p.30)
1. Prevention of waste 2. Atom Economy 3. Less Hazardous Chemical Synthesis 4. Designing Safer Chemicals 5. Safer Solvents and Auxiliaries 6. Design for Energy Efficiency 7. Use of Renewable Feedstocks 8. Reduce Derivatives 9. Catalysis 10. Design for Degradation 11. Real-Time analysis for Pollution Prevention 12. Inherently Safer Chemistry for Accident Prevention
27
Audience Survey Question ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT
For you, how many essential pillars are contained in the 12 principles? • 1 • 2 • 3 • 4 • 5 28
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2/16/2017
THE 3 PILLARS OF GREEN CHEMISTRY renewable obtained from an
eco-respectful process demonstrating a favorable
environmental impact 29
RENEWABLE RAW MATERIALS FIRST PILLAR RENEWABLE = if carbon content from renewable source is above 50% of its total carbons. >> new ISO Guidelines on Natural and Organic Cosmetic ingredients and products To date 52 % (by volume) of all Raw Material Portfolio are from renewable origin 30
30
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OUR RENEWABLE RAW MATERIALS FIRST PILLAR
52% (2016) by volume of our Raw Materials from renewable origin:
1400 Raw Materials 290 Botanical species 60 Countries
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FIRST & SECOND PILLARS
NATURALNESS INDEX = ORIGIN INDEX + DENATURATION INDEX
https://www.youtube.com/watch?v=svc9givqhe0 32 L’Oréal Naturalness Index
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ORIGIN & NATURALNESS INDEXES FIRST & SECOND PILLAR Plant (Organics/wild)
Plant Farming
Animal
Fossil
Mineral
5
4
3
2
1
No inf.
5
4
3
2
1
No inf.
O.I. = ORIGIN INDEX
+ D.I. = DENATURATION INDEX
=
CRUDE
N.I. = NATURALNESS INDEX SLIGHTLY EXTRACTION WITHOUT DENATURING PETROCHEMICAL SOLVENT PROCESS ORIGIN INDEX RENEWABLE ORIGIN ≥ 4 NATURALNESS INDEX : NATURAL ORIGIN ≥ 3.8 NATURALNESS INDEX : NATURAL ≥ 4
MIXTURE INTEGRATING FOSSIL RM STRONGLY DENATURING PROCESS
GREEN CHEMISTRY RAW MATERIAL/NATURAL ORIGIN N.I.= 3.8 O.I.= 4 or 5 with D.I..= 3
33
SOME OF OUR METRICS TOWARDS GREEN CHEMISTRY PROCESS SECOND PILLAR ATOM ECONOMY =
Molecular mass of the desired product /by the molecular mass
of all reactants (x 100%)
E-FACTOR =
amount of waste generated by kg (or ton) of the final ingredient during its manufacture (R. Sheldon, Green Chem., 2007, 9, 1273-1283)
We need calculation of the E-FACTOR with and without water if it is possible, in order, notably, to evaluate water consumption
34
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THE NEW FORMULA REDUCES THE ENVIRONMENTAL FOOTPRINT THIRD PILLAR
IMPROVING THE % OF BIODEGRADABILITY
LOWERING THE WATER FOOTPRINT
+ O2
+
+ CO2
+ H2O
https://www.youtube.com/watch?v=h6MYI5JFDGo L’Oréal assessment of Water Footprint 35
GREEN CHEMISTRY PASSPORT THREE PILLARS = RENEWABLE + ECO-RESPECTFUL PROCESS + NO UNFAVORABLE ENVIRONMENTAL IMPACT E-FACTOR
NB OF STEPS WITH EXTREME CONDITIONS ( 150°C OR >10H) 36
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RENEWABLE INGREDIENTS DEVELOPMENT
37
37 37
DID YOU KNOW IT?
L'Oréal was the 1st company to launch on the market eco‐designed C‐GLYCOSIDE 38
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2/16/2017
39
RENEWABLE INGREDIENTS DEVELOPMENT Collaborations with suppliers on BIOBASED PRODUCTS
O.I. = 4 D.I. = 3 N.I. = 3.8
xylose
rhamnose
mannose
40
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2/16/2017
R1 R4O R3O
R5 O OH
R2
Ideal building blocks Sustainable starting materials Green chemistry compatible Ecofriendly final products Non toxic
TO IMPROVE & DISCOVER NEW BENEFITS 41
Is L’OREAL chemistry able to reach 1, 2 …. or all these goals ?
?
Straightforward routes
? No protecting group
?
Eco-friendly solvents
? ?
RENEWABLE STARTING MATERIALS
ECO-FRIENDLY PROCESSES
ENVIRONMENTAL & HUMAN SAFETY
?
42
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2/16/2017
But before chemistry a little bit of biology…….. Key components of the skin extracellular matrix are : Glycosaminoglycans GAGs, Proteoglycans PGs, Collagens, Elastin PROTEOGLYCAN (PG)
SUGAR LINKER
GLYCOSAMINOGLYCAN
Core protein
uronic acid Galactose Galacto
Xylose
se
HO
?
HN
O O
O HO
O
Xylose
O
Serine
O O H O R 2 mimic H O R 1 C g l y c o s i d e 43
DETECTION OF A NEW GREEN PROCESS: Formation of C-glycosides by a tandem Knoevenagel/Michael in H2O O
O
C H
H 3 C
O H R 3 O
N a H C O O
R H O
2
O H
O H
3
H 2O
1
R
3
R 3 O
9 0 °C 9 H - 1 2 H
O
R
1
R
H O
C H 2
3
O
- C - g ly c o s id e
( g lu c o s e , m a n n o s e , c e llo b io s e )
Opening on access to β-C-glycosides / One-step synthesis Reaction in water / Applicable to various saccharides (mono and disaccharides) Limited scope of activated methylene nucleophiles Lubineau A. et al., Chem. Commun. 2000, 2049-2050
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SUGARS: a wide platform for SYNTHETIC CHEMISTRY Mono-functional C-glycoside A
R
O
R
?
OH
O
HO
CH2 n
OH
HO
OH
n
OH
OH n=0,1
Di-functional C-glycoside
n=0,1
A ROC H A *
How to open the chemical space towards
H O
new C-glycosides without using any protecting group?
n O H
O H n = 0 , 1
45
Opening the chemical space of C-glycosides mono-functional C-xylosides 1. Reduction
O OH
HO
OH
4. Aldol condensation
O O H
H O
O
2. Oxime formation
OH
HO
O H
OH
R
O O
OH
OH
3. Reductive amination
OR N
O OH
HO OH WO2014096699 WO2010063948 WO2010067036 WO2010063953
NHR
O OH
HO OH
46
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2/16/2017
Candidate Selected, Developped & Marketed as a New Antiaging Active
O
PROXYLANE TM
H 3 C
O H
O
+ O
O H
H O
H 3 C
O H
H 2O 9 0 °C
C H
O
b a s e
O H O O H
(D -x y lo s e )
3
H 2O
O H
C H
O
c a t. r e d u c tio n
3
O H H O O H
O H
PROXYLANETM Sustainable Starting Material Xylose from Beech Wood Green Process at the 100 t level => efficient synthesis (2 steps), use of water as solvent, use of catalysis E factor 4,9 Ecofriendly Compound: no bioaccumulation and no ecotoxicity Synthesis of Pro-Xylane : A new biologically active C-glycoside in aqueous media M. Dalko-Csiba and al. Biorg. M ed Chem. Letters , 2009, 19 (3), pp. 845-849. L’Oreal Patent : WO2002051828 TM
47
ProXylane™
47
In vivo results
6 month clinical study (versus placebo): Effect on : - overall skin strength - tone - elasticity - smoothness and homogeneity
Launched on the market
Eur. J. Dermatol. 2008, 18, 297 Eur. J. Dermatol. 2008, 18, 36
ProXylane™ at 10% in cosmetic support
48
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2/16/2017
Opening the chemical space (mono-functional C-xylosides)
1. Reduction
O OH
HO
4. Aldol condensation
O
OH
O H
H O
O OH
HO
O H
OH
R
O OH
O
OH
2. Oxime formation
3. Reductive amination
OR N
O OH
HO
NHR
O OH
HO
OH
OH
49
New more potent Candidate Selected O H
O
O
H3C
O H
O
+ O H
H O O H
O H3C
N a H C O H 2O
3
C H
O
9 0 °C 68%
3
O H O O H
(D -x y lo s e )
O H
O M e H
O H
ProXylane
R0064930
Atom economy
75%
81%
% Renewable C
60%
81%
Environmental impact
not ecotoxic
not ecotoxic
1.
O
NaOH aq 50% IPrOH/water 30°C
2 . c a t. r e d u c tio n 6 2 -7 0 %
H O
O M e O H
O H
O H
6 months clinical trial on going
L’Oreal Patents : WO2010067036 & WO 2014096699 50
25
2/16/2017
Opening the chemical space (di-functional C-xylosides) Mono-functional C-glycoside A
R
O
R
?
OH
O
CH2
HO
OH
n
OH
HO
n
OH
n=0,1
OH
Di-functional C-glycoside
n=0,1
A ROC H A *
How to open the chemical space towards new C-glycosides without using any protecting group?
H O
n O H
O H n = 0 , 1
51
Route to hydroxy amides, esters and acids Inspiration from literature: another Knoevenagel/Michael tandem reaction1
N O
OH
N
O
OH
HO
one-pot
Na
N
O
O N
HO
OH
R
O
OH
O
N
O
HO
O
98% Yield
CH3
+
OH
R
+
OH
R
(D-glucose)
Discovery and development of a new synthetic methodology
1 On
Na
OH
without protecting group
without protecting group
O
NaHCO3 w a te r, h e a t
OH
in water
in water
R
O
O N
OH
H2O2 CH3
O
OH
the synthesis of C glycosyl compounds containing double bonds without the use of protecting groups Carbohydrate Res. 1994, 257, pp 81-95
OH
OH
H N
O
w a te r HO
OH
CH3
O
OH
52
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2/16/2017
Improved synthesis for further chemical diversity OH
OH
H N
O HO
OH
R
O
OH
OH
new method
OH
OH
O
OH O OH
HO
HO
OH
H N
HO
O OH
OH
HO
OH
H N
O OH
O OH
H N
O
O OH
HO
OH
OH O
O OH
H N
O
OH
HO
OH
OH
OH
HO
H N
O OH
OH
O HO
O
O OH
OH OH
OH
H N
O
O OH
HO OH
OH
L’Oréal patent pending
53
53
C-glycosides (mimetics of O-glycosides with higher stability) an overview R1 R4 O R3 O
R5 O
Secondary am ines
Alkoxyam ines
Reductive am ination
R2
Aldolisation, reduction
R1 R4 O R3 O
N O R8
O xim es
HO
HO
O
R7 Reduction
R5 O
R1 R4 O R3 O
Pro-Xylane
HN
OH
HO
HO
R2
O
HO HO
O
HO HO
R5 O
R1 R4 O R3 O
R5 O R6 O
R2
O
Am ides OH
OH
R 6 : F, H, M e, Bn
Esters
Diacids
R2 Ketones
O
Lubineau
R1 R4O R3O
R5 O
OH R2 Mono, di or trisaccharides
collab. P. Anastas
R1 R4O R3O
R R5 11 O
R2 Cyclic ketones
R10 R9
R1 R4O R3O
R5 OOH
R2 -Hydroxy-acides O
Amides OH Esters
O
54
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2/16/2017
CONCLUSION & PERSPECTIVES C-glycosides: great knowledge & valuable know-how at L’OREAL
O
OH OH
HO OH
New types of C-glycosides synthetized : More than 300 → SAR studies New reactions discovered New ingredients identified and developed… and further to be launched in the market
55
SHARING BEAUTY WITH ALL INNOVATING SUSTAINABLY AT L’OREAL « We have no desire to do Green Chemistry. We desire to do the best Chemistry, and it happens to be green. »
P. T. Anastas
Science for a Sustainable Society Symposium, McGill
Straightforward routes
No protecting group
almost
Eco-friendly solvents
RENEWABLE STARTING MATERIALS
ECO-FRIENDLY PROCESSES
ENVIRONMENTAL & HUMAN SAFETY
56
56
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2/16/2017
ACKNOWLEDGEMENTS •
L’OREAL Research & Innovation teams (10 years from conception to development and continuous exploration)
•
CHIMEX teams
•
L. RICARD (X-Ray) at Ecole Polytechnique
•
Pr. LUBINEAU’s team at Paris-Sud University
•
Pr ANASTAS’s team at Yale University
57
REFERENCES http://youtu.be/QOi3ja1TaDo
L’Oréal commitment to Green Chemistry
https://www.youtube.com/watch?v=svc9givqhe0 L’Oréal Naturalness Index https://www.youtube.com/watch?v=h6MYI5JFDGo L’Oréal assessment of Water Footprint http://www.sharingbeautywithall.com/fr (accessed 14/02/17). P.T. Anastas and J.C. Warner, Green Chemistry, Theory and practice, Oxford University Press, New-York, 1998, p.30. R.A. Sheldon, “The E factor: fifteen years on”, Green Chem., 2007, 9, 1273. M. Philippe, B. Didillon and L. Gilbert, Green Chem., 2012, 14, 952. Rodrigues, F; Canac, Y; Lubineau, Andre, Chem Comm (2000), (20), 2049-2050 Hersant, Y; Abou-Jneid, R; Canac, Y; Lubineau, A; Philippe, M; Semeria, D; Radisson, X; Scherrmann, M Carbohydr Res (2004), 339(3), 741-745. Q. Zhang, M. Benoit, K. de Oliveira Vigier, J. Barrault, G. Jégou, M. Philippe and F. Jérôme, Green Chem., 2013, 15, 963. M. Philippe, A. Cavezza, P. Pichaud, S. Trouille and M. Dalko-Csiba, Carbohydr. Chem., 2014, 40, 1. J. Hitce, M. Crutizat, C. Bourdon, A. Vivès, X. Marat and M. Dalko-Csiba, Green Chem., 2015, 17, 3756-3761. M. Philippe, B. Didillon and L. Gilbert, Annales des falsifications, de l’expertise chimique & toxicologique, 2016, 985, 3643. 58
29
2/16/2017
“Natural, Sustainable Innovation: L’Oréal’s Commitment to Renewable Materials and Eco-Friendly Processes”
Xavier Marat
David Constable
Group Leader, Advanced Research, L’Oréal
Science Director, Green Chemistry Institute, The American Chemical Society
Michel Philippe L’Oréal Fellow, L’Oréal
Slides available now! Recordings will be available once they are posted.
www.acs.org/acswebinars This ACS Webinar is being co-produced by the ACS Green Chemistry Institute
• Sustainable Chemicals • Flexible Chemical Manufacturing • More Efficient Processes • Green Chemistry Curricula • Circular Economy Considerations
59
• Sustainable Materials • Academic-Industry Collaborations • Chemicals Policy • Cosmetics • And More!
Early Bird Registration will be open from February 15 until April 28, 2017
gcande.org
60
30
2/16/2017
Upcoming ACS Webinars www.acs.org/acswebinars Thursday, February 23, 2017
Fighting Cancer: Epigenetic Targets for Oncology Session 2 of the 2017 Drug Design and Delivery Symposium
Stuart Conway, Professor of Organic Chemistry, University of Oxford Sharan Bagal, Senior Medicinal Chemist, AstraZeneca
Thursday, March 2, 2017
TERA-print: From Academic Discovery to a Commercial Desktop Fab Session 2 of the 2017 Industrial Science Series
Chad Mirkin, Director, International Institute for Nanotechnology Mark Jones, Executive External Strategy and Communications Fellow, Dow Chemical
Contact ACS Webinars® at
[email protected] 61
“Natural, Sustainable Innovation: L’Oréal’s Commitment to Renewable Materials and Eco-Friendly Processes”
David Constable Science Director, Green Chemistry Institute, The American Chemical Society
Xavier Marat Group Leader, Advanced Research, L’Oréal
Michel Philippe L’Oréal Fellow, L’Oréal
Slides available now! Recordings will be available once they are posted.
www.acs.org/acswebinars This ACS Webinar is being co-produced by the ACS Green Chemistry Institute
62
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2/16/2017
How has ACS Webinars® benefited you? Quote in reference to: http://bit.ly/CosmeticChemistry
“This ACS Webinar presented just the right mix of actual chemistry and practical applications to make it worthwhile for every participant. I used to work in the field myself and really appreciated the way the presenter organized the material.”
Frans Zonnevijlle, Consultant at Intex Diagnostika AG, ACS member for 40 years strong!
Be a featured fan on an upcoming webinar! Write to us @
[email protected] 63
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Benefits of ACS Membership Chemical & Engineering News (C&EN) The preeminent weekly news source. NEW! Free Access to ACS Presentations on Demand® ACS Member only access to over 1,000 presentation recordings from recent ACS meetings and select events. NEW! ACS Career Navigator Your source for leadership development, professional education, career services, and much more.
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Upcoming ACS Webinars www.acs.org/acswebinars Thursday, February 23, 2017
Fighting Cancer: Epigenetic Targets for Oncology Session 2 of the 2017 Drug Design and Delivery Symposium
Stuart Conway, Professor of Organic Chemistry, University of Oxford Sharan Bagal, Senior Medicinal Chemist, AstraZeneca
Thursday, March 2, 2017
TERA-print: From Academic Discovery to a Commercial Desktop Fab Session 2 of the 2017 Industrial Science Series
Chad Mirkin, Director, International Institute for Nanotechnology Mark Jones, Executive External Strategy and Communications Fellow, Dow Chemical
Contact ACS Webinars® at
[email protected] 67
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