Natural, Sustainable Innovation: L’Oréal’s …€œNatural, Sustainable Innovation:...

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gcande.org 9

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Considerations

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Collaborations

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ACS GCI Industrial Roundtables

Catalyzing the integration of sustainable and green chemistry and engineering throughout the global chemistry

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Including companies in the

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We convene 40 companies from across the world to focus on the science of sustainable and green

chemistry and its implementation.

We convene 40 companies from across the world to focus on the science of sustainable and green

chemistry and its implementation.

ChemIDP.org 12

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Thursday, February 23, 2017

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“Natural, Sustainable Innovation: L’Oréal’s Commitment to Renewable Materials and Eco-Friendly Processes”

www.acs.org/acswebinars

Slides available now! Recordings will be available once they are posted.

Michel Philippe L’Oréal Fellow,

L’Oréal

David Constable Science Director,

Green Chemistry Institute,

The American Chemical Society

Xavier Marat Group Leader,

Advanced Research, L’Oréal

This ACS Webinar is being co-produced by the ACS Green Chemistry Institute

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NATURAL, SUSTAINABLE INNOVATION:

L’ORÉAL’S COMMITMENT TO RENEWABLE

MATERIALS & ECO-FRIENDLY PROCESSES

Michel PHILIPPE, PhD and Xavier MARAT, PhD - L’Oréal R&I

25.8 Billions € (2016)

countries

people

International brands

205 Products sold every second

140

82,900

32

1st WORLDWIDE COSMETIC GROUP

16

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Hair dye Perfume

Make up Hair care Skincare

ALL THE BEAUTY NEEDS

17

18

About how many patents does L'Oreal hold?

• Almost 250 patents

• Almost 300 patents

• Almost 425 patents

• Almost 500 patents

• Almost 750 patents

Audience Survey Question ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

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3,870 people

497 patents 794M € (2015)

624

2011

582

2010

539

2009

523

2008

680

2012

748

2013

761

2014

RESEARCH & INNOVATION

19

20

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I N N OVAT I N G SUSTAINABLY

DEVELOPPING SUSTAINABLY

P RO D U C I N G SUSTAINABLY

L I V I N G 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 24

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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

26

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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)

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

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For you, how many essential pillars are contained in the 12 principles?

• 1

• 2

• 3

• 4

• 5

Audience Survey Question ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

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renewable

obtained from an eco-respectful process

demonstrating a favorable

environmental impact

THE 3 PILLARS

OF GREEN CHEMISTRY

29

RENEWABLE RAW MATERIALS

RENEWABLE = if carbon content from renewable source is above 50% of its total carbons.

FIRST PILLAR

>> 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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52% (2016) by volume of our Raw Materials from renewable origin:

1400 Raw Materials

290 Botanical species

60 Countries

OUR RENEWABLE RAW MATERIALS FIRST PILLAR

31 31

NATURALNESS INDEX

=

ORIGIN INDEX

+

DENATURATION INDEX

FIRST & SECOND PILLARS

32 32

https://www.youtube.com/watch?v=svc9givqhe0 L’Oréal Naturalness Index

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O.I. = ORIGIN INDEX

Plant (Organics/wild)

Plant Farming Mineral

Fossil

Animal

D.I. = DENATURATION INDEX

5 4 3 2 1 No inf.

5 4 3 2 1 No inf.

CRUDE

EXTRACTION

WITHOUT

PETROCHEMICAL SOLVENT

SLIGHTLY

DENATURING

PROCESS

ORIGIN & NATURALNESS INDEXES

MIXTURE

INTEGRATING

FOSSIL RM

ORIGIN INDEX RENEWABLE ORIGIN ≥ 4

NATURALNESS INDEX : NATURAL ORIGIN ≥ 3.8

STRONGLY

DENATURING

PROCESS

GREEN CHEMISTRY

RAW MATERIAL/NATURAL ORIGIN

N.I.= 3.8

O.I.= 4 or 5

with D.I..= 3

+

= N.I. = NATURALNESS INDEX

NATURALNESS INDEX : NATURAL ≥ 4

FIRST & SECOND PILLAR

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

+ CO2 + H2O

O2 + +

IMPROVING THE % OF BIODEGRADABILITY

LOWERING THE WATER FOOTPRINT

https://www.youtube.com/watch?v=h6MYI5JFDGo L’Oréal assessment of Water Footprint

THIRD PILLAR

35

GREEN CHEMISTRY PASSPORT

NB OF STEPS WITH EXTREME CONDITIONS

(<-15°C OR > 150°C OR >10H)

E-FACTOR

= RENEWABLE + ECO-RESPECTFUL PROCESS + NO UNFAVORABLE ENVIRONMENTAL IMPACT

THREE PILLARS

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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39

Collaborations with suppliers on BIOBASED PRODUCTS

RENEWABLE INGREDIENTS DEVELOPMENT

xylose rhamnose mannose

O.I. = 4 D.I. = 3 N.I. = 3.8

40

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TO IMPROVE & DISCOVER NEW BENEFITS

Ideal building blocks

Sustainable starting materials

Green chemistry compatible

Ecofriendly final products

Non toxic

O

R5

R4

OR

3O

R2

O H

R1

41

No

protecting

group

Eco-friendly

solvents Straightforward

routes

RENEWABLE

STARTING

MATERIALS

ECO-FRIENDLY

PROCESSES

ENVIRONMENTAL

& HUMAN

SAFETY

Is L’OREAL chemistry able to reach 1, 2 …. or all these goals ?

? ? ?

? ?

?

42

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GLYCOSAMINOGLYCAN

Galacto

se

Galactose uronic

acid Xylose

Core protein

PROTEOGLYCAN (PG)

O

OHO

OH

O

NH

O

OXylose

Serine

Key components of the skin extracellular matrix are :

Glycosaminoglycans GAGs, Proteoglycans PGs, Collagens, Elastin

O

OHO

OH

R1

R2

-C-glycoside

?

SUGAR

LINKER

mimic

But before chemistry a little bit of biology……..

43

DETECTION OF A NEW GREEN PROCESS:

Formation of C-glycosides by a tandem Knoevenagel/Michael in H2O

OR

3O

OH

O H

R2

O H

R1

O

C H3

OR

3O

OH

O H

R2

R1

CH3

O O

C H3

N a H C O3

H 2 O

9 0 ° C9 H - 1 2 H

( g l u c o s e , m a n n o s e , c e l l o b i o s e ) - C - g l y c o s i d e

Lubineau A. et al., Chem. Commun. 2000, 2049-2050

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

44

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SUGARS: a wide platform for SYNTHETIC CHEMISTRY

CH2

A

OR

OH

OH

OHn

n=0,1

OHOR

OH

OH

OHn

n=0,1

?

Mono-functional C-glycoside

Di-functional C-glycoside

CH

A

OR

OH

OH

OH

A*

n

n=0,1

How to open the chemical space towards

new C-glycosides without using any protecting group?

How to open the chemical space towards

new C-glycosides without using any protecting group?

45

O

OH O H

O H

O

O

OH O H

O H

N

O R

O

OH O H

O H

N H R

O

OH O H

O H

O

R

O H

O

OH O H

O H

O H

1. Reduction

Opening the chemical space of C-glycosides mono-functional C-xylosides

2. Oxime formation 3. Reductive amination

4. Aldol condensation

WO2014096699 WO2010063948 WO2010067036 WO2010063953

46

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O O H

O H

O HOH

CH3

CH3

O

O

O

O HO HOH

O

C H3 O

O HO HOH

O H

C H3+

H 2 O

9 0 ° C

( D - x y l o s e )

H 2 O

c a t . r e d u c t i o nb a s e

Candidate Selected, Developped & Marketed as a New Antiaging Active

PROXYLANE TM

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

PROXYLANETM

Synthesis of Pro-Xylane TM: 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

47 47

ProXylane™

6 month clinical study (versus placebo):

Effect on :

- overall skin strength

- tone

- elasticity

- smoothness and homogeneity

In vivo results

ProXylane™ at 10% in cosmetic support

Launched on the market

Eur. J. Dermatol. 2008, 18, 297 Eur. J. Dermatol. 2008, 18, 36

48

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O

OH O H

O H

O

O

OH O H

O H

N

O R

O

OH O H

O H

N H R

O

OH O H

O H

O

R

O H

O

OH O H

O H

O H

1. Reduction

2. Oxime formation 3. Reductive amination

4. Aldol condensation

Opening the chemical space (mono-functional C-xylosides)

49

O O H

O H

O HOH

CH3

CH3

O

O

N a H C O3

O

O HO HOH

O

C H3

O

O H

OH O HO H

O H

O M e

O

O H

O M e

H+

H 2 O

9 0 ° C

( D - x y l o s e )

2 . c a t . r e d u c t i o n

6 8 % 6 2 - 7 0 %

1 .

6 months clinical trial on going

L’Oreal Patents : WO2010067036 & WO 2014096699

ProXylane R0064930

Atom economy 75% 81%

% Renewable C 60% 81%

Environmental impact not ecotoxic not ecotoxic

NaOH aq 50%

IPrOH/water 30°C

New more potent Candidate Selected

50

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Opening the chemical space (di-functional C-xylosides)

CH2

A

OR

OH

OH

OHn

n=0,1

OHOR

OH

OH

OHn

n=0,1

?

Mono-functional C-glycoside

Di-functional C-glycoside

CH

A

OR

OH

OH

OH

A*

n

n=0,1

How to open the chemical space towards

new C-glycosides without using any protecting group?

How to open the chemical space towards

new C-glycosides without using any protecting group?

51

Inspiration from literature:

another

Knoevenagel/Michael

tandem reaction1

1 On the synthesis of C glycosyl compounds containing double bonds without the use of protecting groups

Carbohydrate Res. 1994, 257, pp 81-95

N

N

O

O

RO

R

O O H

OH O H

O H

O H

O N

N

O

O O

R

R

O HOH

O H

O H

N a+

N a H C O3

w a t e r , h e a t

98% Yield (D-glucose)

one-pot

without protecting group

in water

Discovery and development

of a new synthetic

methodology O N

N

O

O O

C H3

C H3

O HOH

O H

O H

N a+

O

OO HOH

O H

O H O H

NH

C H3

H2

O2

w a t e r

without protecting group

in water

Route to hydroxy amides, esters and acids

52

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L’Oréal patent pending

O

OH

OH OH

OH

OH

O

OH

O

OH

OH OH

OH

NH

OH

O

O

OH

OH OH

OH

NH

OH

O

O

OH

OH OH

OH

NH

OH

O

O

OH

OH OH

OH

O

NH

O

OH

OH OH

NH

OH

OO

OOH

OH

OH

O

OH

OH

OHOH

NH

O

OH

new

method

O

O H

OH O H

NH

O H

O

O H

R

Improved synthesis for further chemical diversity

53 53

C-glycosides (mimetics of O-glycosides with higher stability) an overview

OH

OHO

R5

R4O

R3O

R2

R1

O

O

R6

O

R5

R4O

R3O

R2

R1

O

OOHOH

OH

OH

OOHOH

OH

OH

OH

O

O

R5

R4O

R3O

R2

R1

NHR

7

O

R5

R4O

R3O

R2

R1

NOR

8

R6: F, H, Me, Bn

Pro-Xylane

Aldolisation,reduction

Reduction

Reductiveamination

Oximes

Amides

Esters

Lubineau

Alkoxy-amines

Secondary amines

Ketones

Diacids

O

R5

R4O

R3O

R2

OH

R1

Mono, di or trisaccharides

O

R5

R4O

R3O

R2

R1

OH

OH

O

O

R5

R4O

R3O

R2

R1

O

R11

R10

R9

Amides

Esters-Hydroxy-acides

Cyclic ketones

collab. P.Anastas

54

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O OH

OH

OH

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

C-glycosides: great knowledge & valuable know-how at L’OREAL

CONCLUSION & PERSPECTIVES

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

No

protecting

group

Eco-friendly

solventsStraightforward

routes

RENEWABLE

STARTING

MATERIALS

ECO-FRIENDLY

PROCESSES

ENVIRONMENTAL

& HUMAN

SAFETY almost

56 56

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• 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

ACKNOWLEDGEMENTS

57

REFERENCES

https://www.youtube.com/watch?v=h6MYI5JFDGo L’Oréal assessment of Water Footprint

https://www.youtube.com/watch?v=svc9givqhe0 L’Oréal Naturalness Index

http://youtu.be/QOi3ja1TaDo L’Oréal commitment to Green Chemistry

P.T. Anastas and J.C. Warner, Green Chemistry, Theory and practice, Oxford University Press, New-York, 1998, p.30.

http://www.sharingbeautywithall.com/fr (accessed 14/02/17).

M. Philippe, B. Didillon and L. Gilbert, Green Chem., 2012, 14, 952.

M. Philippe, A. Cavezza, P. Pichaud, S. Trouille and M. Dalko-Csiba, Carbohydr. Chem., 2014, 40, 1.

R.A. Sheldon, “The E factor: fifteen years on”, Green Chem., 2007, 9, 1273.

J. Hitce, M. Crutizat, C. Bourdon, A. Vivès, X. Marat and M. Dalko-Csiba, Green Chem., 2015, 17, 3756-3761.

Q. Zhang, M. Benoit, K. de Oliveira Vigier, J. Barrault, G. Jégou, M. Philippe and F. Jérôme, Green Chem., 2013, 15, 963.

M. Philippe, B. Didillon and L. Gilbert, Annales des falsifications, de l’expertise chimique & toxicologique, 2016, 985, 36-43.

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.

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“Natural, Sustainable Innovation: L’Oréal’s Commitment to Renewable Materials and Eco-Friendly Processes”

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