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- diformyl thiophene.

Objectives: The purpose of this experiment is to synthesize 3,4-Dibromo-2,5diformyl thiophene.

Theoretical

(1) Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density 1 399.72 1 2.50

(2) 2 64.06 0.32 5.00

(3) 2.25 113.16 0.637 5.63

(4) 1 297.93 0.745 2.50

3.125 1.6M -

0.625 1.019g/cm3

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

(1) Mole Ratio M.W (g/gmol) Mass (g) 1 399.72 1.009

(2) 2 64.06 -

(3) 2.25 113.16 0.642

(4) 1 297.93 -

No.of moles (mmol) Volume (ml) Concentration Density

2.52

5.04

5.67

2.52

3.6 1.4M -

0.630 1.019g/cm3

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

Apparatus

Chemicals

Filter Funnel

Ice

Retort Stand

Silicone oil

Hot Plate

4 Molecular Sieve

1L One-necked, Round Bottom Flask

Calcium hydride

Magnetic Stir Bar

Dichloromethane

Spatula

Procedure:

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- diformyl thiophene.

Objectives: The purpose of this experiment is to synthesize 3,4-Dibromo-2,5diformyl thiophene.

Theoretical

(1) Mole Ratio M.W (g/gmol) Mass (g) No.of moles (mmol) Volume (ml) Concentration Density 1 399.72 1 2.50

(2) 2 64.06 0.32 5.00

(3) 2.25 113.16 0.637 5.63

(4) 1 297.93 0.745 2.50

3.125 1.6M -

0.625 1.019g/cm3

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 Argon inlet flow Dry ice/Acetone Bath Ice/ Water Bath Vacuum Oven

Chemicals Tetrabromothiophene Tetrahydrofuran Butyl Lithium N-formylpiperidine Hydrochloric Acid

Actual

(1) Mole Ratio M.W (g/gmol) Mass (g) 1 399.72 0.9999

(2) 2.2 64.06 -

(3) 2.42 113.16 0.637

(4) 1 297.93 -

No.of moles (mmol) Volume (ml) Concentration Density

2.50

5.50

6.05

2.50

6.11 0.9M -

0.698 1.019g/cm3

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 argon inlet and placed on a hot plate was setup. 2) 0.9999g 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) 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

Note: Experiment was terminated after step 9; no precipitate was formed.

Observations

Step 7: The solution turned yellow/brown.

Step 9: A yellow precipitate was formed.

Results

Small insignificant amounts were present.

Discussion

Conclusion/ Recommendation