Project Title Synthesis of donor-acceptor monomers for conjugated electrochromic polymers

Name of Student :

SIOW WEI JIAN, SAMUEL

Matric No.

1003488B

Care Group

A10D4

Name of Company

Institute of Materials Research and Engineering

Company Supervisor :

Dr CHO CHING MUI

TP Liaison Officer

: Dr WUANG SHY CHYI

Diploma in Chemical Engineering AY 2012/2013

Table of Contents Exp no. Title

Page no.

Date: 25/04/12 Title: Introduction to column chromatography. Objectives: The purpose of column chromatography is to separate complex mixture of compounds. Apparatus Column, 1 Conical Flask, 20 Thin Layer Chromatography plates 1L, One Necked, Round Bottom Flask, 1 Beaker, 3 Chemicals Unknown Chemical Mixture Silica Gel Dichloromethane

Procedures 1. A column was filled up with 250g of silica gel via continuous stirring with dichloromethane/hexane (50:50) v/v batch wise. 2. A filter paper was added to the top of the silica packing. 3. The chemical mixture was loaded into the column via a dropper, drop wise. Ensuring the silica packing remained undisturbed. 4. The column was left to run for 9hrs with continuous addition of solvent. 5. Fractions of eluent were collected in multiple, 50ml conical flask. 6. Using thin layer chromatography, fractions of similar purity were combined in a 1L, one necked, round bottom flask and concentrated on the rotary evaporator. Observations Step 6: A colorless solution was formed. Results One product was collected Discussion Column chromatography is an important chemical laboratory technique for organic synthesis. Many techniques like using a rotary evaporator and using a deuterium lamp to identify eluting products are important to take note in future experiments. Conclusion/Recommendations In future experiments, apparatus should be wash and place in the oven overnight. A reservoir could also be used to reduce repetition instead of refilling eluent.

Experiment 1 Batch 1 Date: 24/4/12 Title: Synthesis of 3,4-Dibromo-2,5- diformylthiophene. Objectives: The purpose of this experiment is to synthesize 3,4-Dibromo-2,5diformylthiophene. Theoretical

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 1 2.50 -

(2) 2 64.06 0.32 5.00 3.125 1.6M -

(3) 2.25 113.16 0.637 5.63 0.625 1.019g/cm3

(4) 1 297.93 0.745 2.50 -

Volume of Tetrahydrofuran: 12ml Volume of 6M, Hydrochloric acid: 6.25ml Apparatus 25ml, three neck, round bottom flask, 1 Magnetic Stir Bar, 1 Rubber Septum, 2 Bubbler, 1 Argon inlet flow Dry ice/Acetone Bath Ice/ Water Bath Vacuum Oven Chemicals Tetrabromothiophene Tetrahydrofuran Butyl Lithium N-formylpiperidine Hydrochloric Acid

Actual

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 1.009 2.52 -

(2) 2 64.06 5.04 3.6 1.4M -

(3) 2.25 113.16 0.642 5.67 0.630 1.019g/cm3

(4) 1 297.93 2.52 -

Volume of Tetrahydrofuran: 12ml Volume of 6M, Hydrochloric acid: 6.25ml Procedures 1) A oven dried, 25ml, three necked, round bottom flask equipped with magnetic stir bar, two rubber septum, with an argon inlet and placed on a hot plate was setup. 2) 1.009g of Tetrabromothiophene and 12ml of tetrahydrofuran was added to the setup. 3) The set up was then cooled to -80oc with a dry ice/acetone bath. 4) 3.6ml of 1.4M butyl lithium was added via a syringe dropwise, taking 15mins. 5) The solution was stirred for another 30mins. 6) 0.630ml of Dry N-formylpiperidine was added to the mixture quickly. 7) The solution was left to warm to ambient temperature overnight. 8) The solution was cooled to 0oc using an ice/water bath. 9) 6.25ml of 6M HCl was added to the mixture Note: Experiment was terminated after step 9; no precipitate was formed. Observations Step 7: The solution turned brown. Step 9: The solution remained brown with a layer of oil on the surface. Results Experiment was not completed. No precipitate form.

Discussion At step 9, a small volume of yellow precipitate should form as an indication that the 3,4-dibromo-2,5-diformylthiophene is formed. However, in this experiment, no precipitate was observed. A possible explanation is the oxidation of butyllithium in air. Using the appropriate amount of butyllithium in this reaction is crucial in the structure of product form. In this case, the amount was substantially lesser than expected. No precipitate was even form in excess of HCl and removal of solvent on the rotary evaporator. Conclusion/ Recommendation In the next experiment, the stopper should be tightly sealed and a larger argon inlet is recommended. Butyllithium volume added should be precise.

Date: 30/4/12 Title: Simple Distillation of Dichloromethane Objective: To obtain dry dichloromethane using simple distillation. Practice setting up of apparatus in the fume hood Chemicals Ice Silicone oil 4 Molecular Sieve Calcium hydride Dichloromethane

Apparatus Filter Funnel Retort Stand Hot Plate 1L One-necked, Round Bottom Flask Magnetic Stir Bar Spatula

Procedures 1) A 1L one-necked round bottom flask, equipped with a magnetic stir bar, condenser and a water cooler pump was filled with 700ml of dichloromethane 2) spatulas of calcium hydride were added into the boiling flask 3) The solution was heated to 39.6C 4) The compound was left to distill for 5 hrs 5) The first few drops of the distillate were disposed 6) The distillate was collected in 250ml round bottom flask Note: The hot plate conditions were set at 460rpm and temperature set point of 39.6 degrees Celsius. Observations The solution was colorless throughout the experiment. Results Dry dichloromethane was collected. Discussion Time taken to distill was very long.

Conclusion/ recommendations The round bottom flask can be wrapped with an insulating material to prevent heat loss to the surroundings. An indicator could also be added to the mixture to identify its collection timing.

Experiment 1 Batch 2 Date: 8/5/12 Title: Synthesis of 3,4-Dibromo-2,5- diformylthiophene. Objectives: The purpose of this experiment is to synthesize 3,4-Dibromo-2,5diformylthiophene. Theoretical

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 1 2.50 -

(2) 2 64.06 0.32 5.00 3.125 1.6M -

(3) 2.25 113.16 0.637 5.63 0.625 1.019g/cm3

(4) 1 297.93 0.745 2.50 -

Volume of Tetrahydrofuran: 12ml Volume of 6M, Hydrochloric acid: 6.25ml Apparatus 50ml, three neck, round bottom flask, 1 Magnetic Stir Bar, 1 Rubber Septum, 2 Bubbler, 1 Nitrogen inlet flow Dry ice/Acetone Bath Ice/ Water Bath Vacuum Oven Chemicals Tetrabromothiophene Tetrahydrofuran Butyl Lithium N-formylpiperidine Hydrochloric Acid

Actual

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 0.9999 2.50 -

(2) 2.2 64.06 5.50 6.11 0.9M -

(3) 2.42 113.16 0.637 6.05 0.698 1.019g/cm3

(4) 1 297.93 2.50 -

Volume of Tetrahydrofuran: 20ml Volume of 6M, Hydrochloric acid: 16ml Procedures 1) A oven dried, 50ml, three necked, round bottom flask equipped with magnetic stir bar, two rubber septum, with an nitrogen inlet and placed on a hot plate was setup. 2) 0.9999g of Tetrabromothiophene and 20ml of tetrahydrofuran was added to the setup. 3) The set up was then cooled to -80oc with a dry ice/acetone bath. 4) The system was left to purge for 1 hr with N2 gas 5) 6.11ml of 0.9M butyl lithium was added via a syringe dropwise, taking 15mins. 6) The solution was stirred for another 30mins at -77 oc. 7) 0.7ml of Dry N-formylpiperidine was added to the mixture quickly. 8) The solution was left to warm to ambient temperature overnight. 9) The solution was cooled to 0oc using an ice/water bath. 10) 16ml of 6M HCl was added to the mixture 11) The solution was left to stir for 45mins at 0oc. 12) The solid was the filtered under vacuum on a Buchner funnel. 13) The residue was left to dry overnight in a vacuum oven. Note: Residue collected was insignificantly small; experiment is void. Observations Step 7: The solution turned yellow/brown.

Step 9: A yellow precipitate was formed. Results Small insignificant amounts were present. Discussion In comparison to the first batch, solids form at step 10 was more significant. However, only a small amount of solid is present after suction filtration on the Buchner funnel, this could be due to the larger mole ration used (1:2.2). the purging time foe the system was also lengthen. Conclusion/ Recommendations A longer reaction time can be given between Butyl Lithium and Tetrabromothiophene.

Experiment 1 Batch 3 Date: 10/5/12 Title: Synthesis of 3,4-Dibromo-2,5- diformylthiophene. Objectives: The purpose of this experiment is to synthesize 3,4-Dibromo-2,5diformylthiophene. Theoretical

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 1 2.50 -

(2) 2.2 64.06 0.32 5.51 3.125 1.6M -

(3) 2.42 113.16 0.686 6.06 0.673 1.019g/cm3

(4) 1 297.93 0.735 2.50 -

Volume of Tetrahydrofuran: 12ml Volume of 6M, Hydrochloric acid: 6.25ml Apparatus 50ml, three neck, round bottom flask, 1 Magnetic Stir Bar, 1 Rubber Septum, 2 Bubbler, 1 Nitrogen inlet flow Dry ice/Acetone Bath Ice/ Water Bath Vacuum Oven Chemicals Tetrabromothiophene Tetrahydrofuran Butyl Lithium N-formylpiperidine Hydrochloric Acid

Actual

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 1.001 2.50 -

(2) 2.2 64.06 5.51 6.11 0.9M -

(3) 2.42 113.16 0.686 6.06 0.698 1.019g/cm3

(4) 1 297.93 0.1686 2.50 -

Volume of Tetrahydrofuran: 20ml Volume of 6M, Hydrochloric acid: 19ml Procedures 1) A oven dried, 50ml, three necked, round bottom flask equipped with magnetic stir bar, two rubber septum, with a nitrogen inlet and placed on a hot plate was setup. 2) 1.001g of Tetrabromothiophene and 20ml of tetrahydrofuran was added to the setup. 3) The set up was then cooled to -78oc with a dry ice/acetone bath. 4) The system was left to purge for 3 hrs with N2 gas 5) 6.11ml of 0.9M butyl lithium was added via a syringe drop wise, taking 15mins. 6) The solution was stirred for another 1hr at -78 oc. 7) 0.7ml of Dry N-formylpiperidine was added to the mixture quickly. 8) The solution was left to warm to ambient temperature overnight. 9) The solution was cooled to 0oc using an ice/water bath. 10) 19ml of 6M HCl was added to the mixture 11) The solution was left to stir for 45mins at 0oc. 12) The solid was the filtered under vacuum on a Buchner funnel. 13) The residue was left to dry overnight in a vacuum oven. Observations Step 8: The solution turned from colorless to yellow. Step 10: A yellow precipitate was formed together with a layer of oil on the surface.

Step 13: A crude brown solid was formed. Results Mass of vial + cap: 22.1015g Mass of vial + cap + solids: 22.2714g Mass of solid: 0.1686g Percentage Yield: 0.1686/0.735*100% = 22.9% Discussion In this experiment, there is a slight variation to the 2nd batch. The time allowed for Butyl Lithium to react was increased from 30minutes to 1 hour. There is also a larger precipitate produced upon the addition of hydrochloric acid. However, the solid collected did not prove to be substantial, this could be due to the decomposition of Butyl Lithium. Conclusion/ Recommendations The reaction is considered complete. However, several improvements like a longer reaction time and the transfer methods of chemical can be reconsidered.

Date: 15/5/12 Title: Determining the Concentration of Butyl Lithium using titration Purpose: Butyl Lithium is a highly reactive compound, it decomposes easily. Titration is required to determine the concentration of butyl lithium. Apparatus 25ml, three necked, Round Bottom Flask, 1 Magnetic Stir Bar, 1 Rubber Septum, 2 Argon Inlet Bubbler Chemicals Biphenyl-4-methanol Unknown concentration Butyl Lithium Tetrahydrofuran

Procedures 1. A 25ml, three necked round bottom flask, equipped with a magnetic stir bar, two rubber septum, stop cocked with an argon inlet was placed on a hot plate. 2. 0.184g (1mol) of biphenyl-4-methanol and 6ml of dried tetrahydrofuran was added to the setup. 3. The system was left to purge for 30 minutes

4. The unknown concentration of Butyl Lithium was added drop wise via a syringe
till the solution change to purple/blue.

Observations Step 2: A cloudy solution was formed. Step 4: The solution turned to purple/blue. Results Volume of Butyl Lithium used to titrate: 1.25ml Concentration of Butyl Lithium: 0.81M Discussion Butyl Lithium is a very highly reactive compound. This titration is only a estimation of the current concentration of Butyl Lithium. The color change to purple/blue is only substantial if it last for more than a minute. Conclusion/ Recommendations A longer purging time is recommended to increase the accuracy of the titration. A syringe with lesser systematic error could be used. Calculations 1 mole of Bi-phenyl-4-methanol reacts with 1 mole of Butyl Lithium

Concentration of Butyl Lithium= (1.25ml/mol)-1=0.81M

Experiment 1 Batch 4 Date: 15/5/12 Title: Synthesis of 3,4-Dibromo-2,5- diformylthiophene. Objectives: The purpose of this experiment is to synthesize 3,4-Dibromo-2,5diformylthiophene. Theoretical

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 2 5.00 -

(2) 2.2 64.06 11.01 13.58 0.9M -

(3) 2.42 113.16 1.3704 12.11 0.673 1.019g/cm3

(4) 1 297.93 1.4897 5.00 -

Volume of Tetrahydrofuran: 25ml Volume of 6M, Hydrochloric acid: 12.5ml Apparatus 100ml, three neck, round bottom flask, 1 Magnetic Stir Bar, 1 Rubber Septum, 2 Bubbler, 1 Nitrogen inlet flow Dry ice/Acetone Bath Ice/ Water Bath Vacuum Oven Chemicals Tetrabromothiophene Tetrahydrofuran Butyl Lithium N-formylpiperidine Hydrochloric Acid

Actual

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 2.0001 5.00 -

(2) 2.2 64.06 11.01 13.5 0.81M -

(3) 2.42 113.16 1.3704 12.11 1.4 1.019g/cm3

(4) 1 297.93 No yield 5.00 -

Volume of Tetrahydrofuran: 35ml Volume of 6M, Hydrochloric acid: 40ml Procedures 1) A 100ml, three necked, round bottom flask equipped with magnetic stir bar, two rubber septum, with an argon inlet and placed on a hot plate was setup. 2) 2.0001g of Tetrabromothiophene and 35ml of tetrahydrofuran was added to the setup. 3) The set up was then cooled to -77oc with a dry ice/acetone bath. 4) The system was left to purge for 30mins with Argon gas 5) 13.5ml of 0.81M butyl lithium was added via a syringe drop wise, taking 20mins. 6) The solution was stirred for another 2hours at -78 oc. 7) 1.4ml of Dry N-formylpiperidine was added to the mixture quickly. 8) The solution was left to warm to ambient temperature overnight. 9) The solution was cooled to 0oc using an ice/water bath. 10) 40ml of 6M HCl was added to the mixture Note: Experiment stopped at step 10; no precipitate formed Observations Step 7: The solution turned from colorless to yellow. Step 8: The solution turned from yellow to reddish brown. Step 10: A layer of oil was present on the surface of the liquid. No particulates were present.

Results Experiment was not completed. No precipitate form Discussion At step 8, the solution turned reddish brown. This is different from all the previous experiments; this could be because the solution may not have reacted, when the butyl lithium was added. No particulates were present in step 10 showing that majority of the starting materials were unreacted/underreacted. Conclusion/ Recommendations Butyl lithium could be added in a longer duration of time and left to react for a longer period of time.

Experiment 1 Batch 5 Date: 16/5/12 Title: Synthesis of 3,4-Dibromo-2,5- diformylthiophene. Objectives: The purpose of this experiment is to synthesize 3,4-Dibromo-2,5diformylthiophene. Theoretical

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 2 5.00 -

(2) 2.2 64.06 11.01 13.58 0.9M -

(3) 2.42 113.16 1.3704 12.11 0.673 1.019g/cm3

(4) 1 297.93 1.4897 5.00 -

Volume of Tetrahydrofuran: 25ml Volume of 6M, Hydrochloric acid: 12.5ml Apparatus 100ml, three neck, round bottom flask, 1 Magnetic Stir Bar, 1 Rubber Septum, 2 Bubbler, 1 Nitrogen inlet flow Dry ice/Acetone Bath Ice/ Water Bath Vacuum Oven Chemicals Tetrabromothiophene Tetrahydrofuran Butyl Lithium N-formylpiperidine Hydrochloric Acid

Actual

Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density

(1) 1 399.72 1.9998 5.00 -

(2) 2.2 64.06 11.01 13.58 0.81M -

(3) 2.42 113.16 1.3704 12.11 1.4 1.019g/cm3

(4) 1 297.93 0.1637 5.00 -

Volume of Tetrahydrofuran: 38ml Volume of 6M, Hydrochloric acid: 40ml Procedures 1) A 100ml, three necked, round bottom flask equipped with magnetic stir bar, two rubber septum, with an argon inlet and placed on a hot plate was setup. 2) 1.9998g of Tetrabromothiophene and 38ml of tetrahydrofuran was added to the setup. 3) The set up was then cooled to -78oc with a dry ice/acetone bath. 4) The system was left to purge for 2 hours with Argon gas 5) 13.5ml of 0.81M butyl lithium was added via a syringe drop wise, taking 20mins. 6) The solution was stirred for another 2hours at -78 oc. 7) 1.4ml of Dry N-formylpiperidine was added to the mixture quickly. 8) The solution was left to warm to ambient temperature overnight. 9) The solution was cooled to 0oc using an ice/water bath. 10) 40ml of 6M HCl was added to the mixture 11) The solution was left to stir for 45mins at 0oc. 12) The solid was the filtered under vacuum on a Buchner funnel using suction filtration. 13) The residue was left to dry overnight in a vacuum oven Note: The solid was left to dry for 5 days in vacuum oven. Observations Step 7: The solution turned from colorless to yellow.

Step 10: A yellow precipitate was formed and a layer of oil was present on the surface. Step 13: A crude brown solid was formed. Results Mass of vial + cap: 21.9936g Mass of vial + cap + solids: 22.1573g Mass of solid: 0.1637g Percentage Yield: 0.1637/1.4897*100% = 10.99%

Discussion Conclusion/ Recommendations