Recent Advances in Organic Chemistry by

Academia Using Real-Time In Situ FTIR -

Part V

Presenter: Paul SchollSenior Technical Manager:

Reaction Analysis

Forewords

Previous “recent advances in academia” webinars

- “Review of Recent Advances in Organic Chemistry Using Real-Time In Situ FTIR

– Part I”, Jennifer Andrews, April 2009

- “Recent Advances in Organic Chemistry by Academia Using Real-Time In Situ

FTIR – Part II”, Paul Scholl, June 2009

- “Recent Advances in Organic Chemistry in Academia Using Real-Time In Situ

FTIR – Part III”, Paul Scholl, October 2009

- “Recent Advances in Organic Chemistry in Academia Using Real-Time In Situ

FTIR – Part IV”, Dominique Hebrault, March 2010

Forewords

Past ReactIR™ technology webinars

- “Application of Quantitative Analysis to Predict Absolute Concentration Information

in Real-time”, Jon Goode, 2009

- “Extracting Critical Information from Challenging Reaction Data Sets”, Paul Scholl,

2009

- “Best Practices for the Characterization of Organic Reactions Using Real-time In

Situ FTIR”, Jennifer Andrews, 2009

- “Introduction to Reaction Analysis Using Real-time In Situ FTIR”, Will Kowalchyk,

2009

- “Innovations in Reaction Analysis”, Paul Scholl, 2007

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Selected Publications for Part V

Online Monitoring of Biotransformations in High Viscous Multiphase

Systems by Means of FT-IR and Chemometrics

Tuning the Selectivity of the Oxetane and CO2 Coupling Process

Catalyzed by (Salen)CrCl/n-Bu4NX: Cyclic Carbonate Formation vs

Aliphatic Polycarbonate Production

Equimolar CO2 Absorption by Anion-Functionalized Ionic Liquids

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Introduction

Online Monitoring of Biotransformations in High Viscous Multiphase

Systems by Means of FT-IR and Chemometrics

Andreas Liese et al; Institute of Technical Biocatalysis, Hamburg

University of Technology, Germany

Mettler-Toledo AutoChem, Inc., Columbia, MD, USA

Evonik Goldschmidt GmbH, Essen, Germany

Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

Quantitative Prediction in Problematic Matrix

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Unstable

emulsion system

Quantitative

analysis difficult

Four dispersed

phases

Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

Solvent Free Esterifications using Biocatalyst

“Green Chemistry”

- No solvents

- Reduced energy demands

- Real-time analysis

Prevents waste

Solvent free esterification

yielding myristyl myristate

Solvent free esterification

yielding polyglycerol-3-

laurate

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Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

Correlate Off-line Data to Reaction Progress

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Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

Quantitative Diagnostics Indicate Good Fit

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Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

Conversion Predicted in Real-time

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Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

Acid Value Predicted in Real-time

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Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

Online FTIR Predicts Where Off-line Fails

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Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

Conclusions

Real-time FTIR gives reliable quantitative information for the

esterifications of fatty esters in highly viscous solvent free systems

Solid particles and gas bubbles did not have any significant influence

on the spectral data

Online analysis of biotransformations in emulsion systems of up to four

phases is possible

Unstable two phase systems can be predicted where they could not

have been in the past

Additional advantage include:

- No volume loss by sampling

- No catalyst loss by sampling

- Automated live analysis in complicated systems

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Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

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Introduction

Tuning the Selectivity of the Oxetane and CO2 Coupling Process

Catalyzed by (Salen)CrCl/n-Bu4NX: Cyclic Carbonate Formation vs

Aliphatic Polycarbonate Production

Donald J. Darensbourg* and Adriana I. Moncada

Department of Chemistry, Texas A&M University, College Station, Texas

77843

Source: Macromolecules, 2010, 43 (14), pp 5996–6003

Introduction

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Source: Macromolecules, 2010, 43 (14), pp 5996–6003

Biodegradable aliphatic

polycarbonates are important

components of non-toxic

thermoplastic elastomers

Alternative copolymerization of

CO2 and aliphatic epoxide such as

propylene oxide in the presence of

metal-based catalyst has shown

significant advances

There are economic and

environmental benefits arising from

the use of biorenewable carbon

dioxide

Oxetane + CO2 Copolymerization Reaction

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Source: Macromolecules, 2010, 43 (14), pp 5996–6003

Complex 1

Oxetane (Ring Opening Polymerization)

TMC (Trimethylene Carbonate)

Effect of Cocatalyst Species

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Source: Macromolecules, 2010, 43 (14), pp 5996–6003

TMC Formation Rates

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Source: Macromolecules, 2010, 43 (14), pp 5996–6003

Poly(TMC) and TMC Formation with Temperature

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Source: Macromolecules, 2010, 43 (14), pp 5996–6003

Poly(TMC)

TMC

Conclusions

(Salen)CrCl complex along with n-Bu4NX (X = Br, I) is an

effective catalyst system for the selective coupling of

oxetane and CO2

Provides the corresponding polycarbonate with minimal

amounts of ether linkages at 110 C

Selectivity of the oxetane and CO2 coupling process can

be tuned by altering the nature of the anionic-based

cocatalyst

Anions that are good leaving groups such as bromide

and iodide, are more effective at yielding trimethylene

carbonate

Real-time in situ FTIR provided key information about

reaction rates under pressure without upsetting reaction

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Source: Macromolecules, 2010, 43 (14), pp 5996–6003

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Introduction

Equimolar CO2 Absorption by Anion-Functionalized Ionic Liquids

Burcu E. Gurkan, Juan C. de la Fuente,† Elaine M. Mindrup, Lindsay E.

Ficke, Brett F. Goodrich, Erica A. Price, William F. Schneider,* and Joan

F. Brennecke*

Department of Chemical and Biomolecular Engineering, University of Notre

Dame, Notre Dame, Indiana 46556

Source:: JACS 2010, 132, 2116 – 2117

Introduction

Materials that selectively and efficiently absorb CO2

from flue gases is essential to realizing practical

carbon capture and sequestration

Ionic liquids are promising because of their negligible

vapor pressures, high thermal stability and virtually

limitless chemical tunability

Anion functionalized ionic liquids can obtain extremely

high capacity for CO2 (one mole of CO2 per mole of IL)

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Source:: JACS 2010, 132, 2116 – 2117

Confirmation of 1:1 Stoichiometry

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Source:: JACS 2010, 132, 2116 – 2117

CO2 Reacted with [P66614][Met]

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Source:: JACS 2010, 132, 2116 – 2117

Fraction of Dissolved vs. Reacted CO2

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Source:: JACS 2010, 132, 2116 – 2117

List of Additional Publications

Organometallics 2007, 26, 1134-1142

Org. Lett., Vol. 10, No. 13, 2008

J. of Supercritical Fluids 46 (2008) 218–225

Analytical Biochemistry 385 (2009) 187–193

Applied Catalysis A: General 264 (2004) 1–12

Inorganic Chemistry, Vol. 47, No. 21, 2008

Inorg. Chem. 2009, 48, 7787–7793

Chem. Mater. 2008, 20, 7022–7030

Chemical Engineering Research and Design 87 (2009) 97–101

J. Am. Chem. Soc. 2008, 130, 15602–15610

Internal usage only

Questions and Answers

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OR

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OR

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19, 2010 in Baltimore, MD, USA – www.mt.com/ipdc

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