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ID 15201XX

A THESIS SUBMITTED TO

VIDYASIRIMEDHI INSTITUTE OF SCIENCE AND TECHNOLOGY

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR

THE DEGREE OF MASTER OF ENGINEERING

IN MATERIALS SCIENCE AND ENGINEERING

201X

Title Xxxxxxxxxxxxxx Xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx

Xxxxxxxxxxxxxxxxxxxxxxxxxx

Advisor Asst. Prof. Dr. Xxxx Xxxx

Name Ms. Xxxx Xxxx

Program Master of Engineering Program in Biomolecular Science and Engineering

(International Program)

Examination Date XX January 20XX

Vidyasirimedhi Institute of Science and Technology approved this thesis as a partial

fulfillment of the requirements for the degree of Master of Biomolecular Science and

Engineering.

Examination Committee:

…………………………… Chairperson ……………………………… Member

(Asst. Prof. Dr. Rojana Pornprasertsuk) (Asst. Prof. Dr. Xxxxxxxx Xxxxxx)

……………………………… Member ……………………………… Member

(Asst. Prof. Dr. Valerio D’Elia) (Asst. Prof. Dr. Xxxxxxxx Xxxxxx)

……………………………… Member

(Dr. Kanokwan Kongpatpanich)

………………………………………..

(Prof. Dr. Jumras Limtrakul)

Chairperson

Graduate Studies Committee

ii

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Abstract

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Keywords: Two-component catalyst systems, hydrogen bond donors, organocatalysts,

cyclic carbonates, conversion of CO2

iii

Acknowledgement

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XXXXXX XXXXXXX

7 October 2017

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Contents

Page

Abstract........................................................................................................................... ii

Acknowledgement ......................................................................................................... iii

List of Tables ................................................................................................................. vi

List of Figures................................................................................................................ vi

List of Abbreviations ...................................................................................................... x

Chapter 1 Introduction .................................................................................................... 2

1.1 O2 as a Raw Material ...................................................................................... 2

1.2 Synthesis of Cyclic Carbonates from CO2 ................................................... 6

1.3 Coupling of CO2 and epoxides by using homogeneous organocatalysts . 6

Chapter 2 Objectives ...................................................................................................... 8

Chapter 3 Literature Reviews ......................................................................................... 9

3.1 Alcohols ............................................................................................................ 9

3.2 Saccharides..................................................................................................... 11

3.3 Silanols ........................................................................................................... 12

3.4 Phenol and derivatives .................................................................................. 12

3.5 Carboxylic acids ............................................................................................ 15

Chapter 4 Materials and Methods................................................................................. 17

4.1 General information ...................................................................................... 17

4.2 Experimental procedures ...................... Error! Bookmark not defined.17

4.2.1 Catalysts screening ............................................................................. 18

4.2.2 Effect of water..................................................................................... 18

4.2.3 Catalytic activity for substrate scope ............................................... 18

4.3 In situ IR experiments and additional catalysis data ................................ 20

4.4 1H NMR investigation of L-ascorbic acid-epichlorohydrin solutions .... 21

Chapter 5 Results and Discussion ................................................................................ 22

5.1 Catalysts screening ........................................................................................ 22

5.2 Effect of water ............................................................................................... 29

5.3 Scope of the Substrate .................................................................................. 30

v

Contents (Cont.)

Page

5.4 The effect of reaction parameters ................................................................ 32

5.5 In situ IR experiments and additional catalysis data ................................ 34

5.6 1H NMR investigation of L-ascorbic acid-epichlorhydrin solutions ...... 37

Chapter 6 Conclusion ................................................................................................... 40

References .................................................................................................................... 42

Appendix ..................................................................................................................... 51

Author’s Biography ...................................................................................................... 52

vi

List of Tables

Table Page

4.1 Chemical Shifts (δ, ppm, CDCl3) for the corresponding

OCH2CHR protons in the epoxides and in the carbonate

products

20

5.1 The screening of several hydrogen bond donors/

nucleophiles dual-organocatalyst for the coupling of CO2

with epichlorohydrin

23

5.2 The catalytic effect of other sugars selection/ TBAI dual-

organocatalyst for the coupling of CO2 with epichlorohydrin

27

5.3 Cycloaddition of CO2 to various substrates catalysed by L-

ascorbic acid, D-fructose, or phenol /TBAI dual

organocatalysts

31

5.4 Cycloaddition of CO2 to various epoxides catalysed by L-

ascorbic acid/TBAI.

33

5.5 Comparison of catalytic activity between L-ascorbic

acid/TBAI and YCl3/TBAI in the presence or in the absence

of water (10 mol%)

36

5.6 Chemical shifts of the protons of L-ascorbic acid and

epichlorohydrin for the spectra presented in Figures 5.8 and

5.9

39

vii

List of Figures

Figure Page

1.1 Several chemical reactions involving CO2 transformation 3

1.2 Synthesis of cyclic carbonate from CO2 and epoxide

cyclization

3

1.1 Synthetic routes to produce cyclic carbonates 4

1.4 Number of publications between 1950 and 2015 for

synthesis of cyclic carbonate in Scifinder

5

1.5 A proposed reaction pathway of bi-component

organocatalysts

7

3.1 Computed free energy surface for glycidol/ CO2 coupling

promoted by TBAB.

9

3.2 Plausible mechanism of the cycloaddition of CO2 in the

presence of vicinal diols.

10


presence of saccharide/DBU as dual organocatalyst

11


presence of silanediol/TBAI as dual organocatalyst.

12

3.5 Synthesis of cyclic carbonate from CO2 and terminal

epoxides by using p-methoxyphenol /DMAP as dual

organocatalyst

13


epoxides catalysed by TBAB in the presence of phenol and

1,2-benzenedio

13

3.7 Schematic structures of tannic acid 14

3.8 Schematic structures of gallic acid 15


epoxides catalyzed by KI in the presence of HCOOH.

15

viii

List of Figures (Cont.)

Figure Page

3.10 Plausible mechanism of cyclic carbonate from CO2 and

epoxides catalyzed by DMAP in the presence of acetic acid

16

5.1 General organocatalytic activation mechanism for the

synthesis of cyclic carbonate

22

ix

List of Abbreviations

HBD Hydrogen Bond Donor

TBAB Tetra-N-butyl ammonium bromide

TBAI Tetra-N-butyl ammonium iodide

DMAP 4-(dimethylamino)pyridine

DBU 1,8-diazabicyclo [5.4.0]-7-undecene

DABCO 1,4-diazabicyclo [2.2.2] octane

PO Propylene oxide

PC Propylene carbonate

Chapter 1

Introduction

1.1 Heading

The chapter headings should be 14 points and any other titles should be in 12

points. The text in the chapter body should be computer printed in 12 points Times New

Roman font.

1.1.1 Sub-heading 1

Typing should be with a spacing of 1. 5 between lines, including the List

of References and Appendices. Xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx.

1.1.1.1 Sub-heading 2

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Chapter 2

Literature Reviews

2.1 The table and figure numbers

The table and figure numbers shall represent the chapter numbers. For example,

the first table in the Chapter 2 shall be “Table 2.1 …………………….”, etc. Number

and title of a table ( Table caption) should be placed ABOVE the table and align left.

The word “Table 2.1” is bold font except its caption.

Table 2.1 .........................................

Header Header Header Header Header

Body

Body

Body

Chapter 3

Methodology and Methods

3.1 Figure

The figure numbers shall represent the chapter numbers. For example, the first

figure in the Chapter 3 shall be “Figure 3.1 ………….”, etc. Number and title of a figure

( Figure caption) should be placed BELOW the figure. For the figure caption which

contains only 1 line, it should align CENTER throughout the thesis. For the figure

caption which contains more than 1 line, it should align left throughout the thesis.

Figure 3.1 Schematic structures of tannic acid

8

Figure 3.2 Number of publications between 1950 and 2015 for synthesis of cyclic

carbonate in Scifinder

9

Chapter 4

Results and Discussion

4.1 Citation

Please follow the VISTEC Vancouver Style for your citation on the thesis.

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Chapter 5

Conclusion

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submitting to the Graduate Studies. Please follow the process for submitting your

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11

References

1. Sopeña S, Fiorani G, Martín C, Kleij AW. Highly Efficient organocatalyzed

conversion of oxiranes and CO2 into organic carbonates. ChemSusChem.

2015;8(19):3248-54.

2. Ansell J, Hirsh J, Poller L, Bussey H, Jacobson A, Hylek E. The pharmacology and

management of the vitamin K antagonists. Chest. 2004;126:204S.

3. Bell RG, Caldwell PT. Mechanism of warfarin resistance. Warfarin and the

metabolism of vitamin K1. Biochemistry. 2000;12(9):1759-62.

4. Cai K, Shen W, Ren BY, He J, Wu SZ, Wang W. A phytic acid modified CoFe2O4

magnetic adsorbent with controllable morphology, excellent selective adsorption

for dyes and ultra-strong adsorption ability for metal ions. Chem Eng J.

2017;330:936-46.

5. Coleman WF. Molecular Models of Warfarin and Related Compounds. J Chem

Educ. 2010;87(2):229-.

6. Cui G-H, Wang Z, Yang Y-C, Tian S-W, Yue J. Heterogeneous game resource

distributions promote cooperation in spatial prisoner’s dilemma game. Physica A:

Statistical Mechanics and its Applications. 2018;490:1191-200.

7. Du CF, Xue YT, Wu ZS, Wu ZL. Microwave-assisted one-step preparation of

macadamia nut shell-based activated carbon for efficient adsorption of Reactive

Blue. New J Chem. 2017;41(24):15373-83.

8. Karlsson BCG, Rosengren AM, Andersson PO, Nicholls IA. Molecular insights on

the two fluorescence lifetimes displayed by warfarin from fluorescence anisotropy

and molecular dynamics studies. J Phys Chem B. 2009;113:7945.

9. Krishna KA, Vishalakshi B. Gellan gum-based novel composite hydrogel:

Evaluation as adsorbent for cationic dyes. J Appl Polym Sci. 2017;134(47).

10. Li T, Chang CY, Jin DY, Lin PJ, Khvorova A, Stafford DW. Identification of the

gene for vitamin K epoxide reductase. Nature. 2004;427:541.

11. Mahidol University. Reconfiguring Faculty Roles for Virtual Settings.

2012;73(1):123-40.

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12. Rosengren AM, Karlsson BCG, Näslund I, Andersson PO, Nicholls IA. In situ

detection of warfarin using time-correlated single-photon counting. Biochem

Biophys Res Commun. 2011;407:60.

13. Sharma V, Chandra F, Sahoo D, Koner AL. Efficient Microwave-Assisted

Synthesis of Sonogashira-Coupled Perylene Monoimide Derivatives: Impact of

Electron-Donating Groups on Optoelectronic Properties. Eur J Org Chem.

2017(46):6901-5.

14. Shi F, Li GX, Zhou ZJ, Xu RD, Li WK, Zhuang WH, et al. Microwave ablation

versus radiofrequency ablation for the treatment of pulmonary tumors. Oncotarget.

2017;8(65):109791-8.

15. Tsuchiya Y, Hamashima Y, Sodeoka M. A New Entry to Pd−H Chemistry:

Catalytic Asymmetric Conjugate Reduction of Enones with EtOH and a Highly

Enantioselective Synthesis of Warfarin. Org Lett. 2000;8(21):4851-4.

16. Unge P, Svedberg LE, Nordgren A, Blom H, Andersson T, Lagerström PO, et al.

A Study of the interaction of omeprazole and warfarin in anticoagulated patients.

Br J Clin Pharmacol. 1992;34:509.

17. Zheng J, Shamsi SA. Combination of Chiral Capillary Electrochromatography with

Electrospray Ionization Mass Spectrometry: Method Development and Assay of

Warfarin Enantiomers in Human Plasma. Anal Chem. 2000;75(22):6295-305.

13

Author’s Biography

Name: XXXXX XXXXXX

Date of birth: February 19th, 1993

Place of birth: Bangkok, Thailand

Current Address: 33/6 Xxxxxxx, Xxxxx, Xxxxxx 12110

Education: Bachelor’s Degree in Chemistry, Thammasat University,

Pathumthani, Thailand (2011-2014)

Master’s degree in Materials Science and Engineering,

Vidyasirimedhi Institute of Science and Technology,

Rayong, Thailand (2015-2017)

Scholarship: Recipient of the full scholarship from Vidyasirimedhi

Institute of Science and Technlogy (VISTEC)

Academic publication: XXXXXX X, Shamsi SA. Combination of Chiral

Capillary Electrochromatography with Electrospray

Ionization Mass Spectrometry: Method Development

and Assay of Warfarin Enantiomers in Human Plasma.

Anal Chem. 2000;75(22):6295-305.

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