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SYNTHESIS OF BENZOIN

ELIZABETH HACKETT ORGANIC CHEMISTRY II DR. JONES 11/12/13

PURPOSE
The purpose of this experiment is to investigate the underlying principles of green chemistry and to successfully perform a condensation reaction to form benzoin using the environmentally friendly catalyst, thiamine.

THEORY
In the experiment, we synthesized benzoin from benzaldehyde. Benzaldehyde does not possess -hydrogens and therefore does not undergo self-aldol condensation. However, in the presence of a catalyst such as thiamine, benzaldehyde undergoes a unique self-condensation reaction, called benzoin condensation, which involves sequential nucleophilic additions to the carbonyl groups of two benzaldehyde molecules. This coupling reaction between two aldehydes allows for the successful preparation of -hydroxyketones. The first step of the experiment involves the formation of a nucleophilic catalyst. Thiamine is deprotonated by the base, sodium hydroxide, forming the thiazolium ion, which is a stabilized carbene. The formation of the nucleophilic catalyst is shown in the reaction below:

Next, the negatively-charged carbon on the thiazolium ion, acting as a nucleophile, attacks the electrophilic carbon of the benzaldehyde carbonyl, forming the alkylated thiazole intermediate shown in the reaction mechanism below: Nucleophilic Carbonyl Addition

This forms an oxygen anion, which will deprotonate water to form a hydroxyl group. Due these resonance effects in the thiazole ring, the benzylic hydrogen is now acidic enough to be removed by the base present in the reaction, and the base subsequently deprotonates the carbon with the hydroxyl group to form a carbanion. This part of the reaction mechanism is shown below:

Now, the first benzaldehyde molecule, assisted by thiamine, can finally act as a nucleophile and it attacks the carbonyl of a second benzaldehyde, forming another oxyanion. The oxyanion will deprotonate water to form another hydroxyl group. The base will then deprotonate the hydroxyl group attached to the carbon that is adjacent to the thiazole ring. This will result in the elimination of the thiazolium ion catalyst and formation of our product, benzoin. The mechanism of these reaction steps are shown below:

The benzoin condensation reaction is catalyzed by a nucleophile, such as the cyanide anion or an N-heterocyclic carbene. Previous methods of synthesis usually involved cyanide ion, which is known to be highly toxic and not environmentally friendly. Thus, the replacement of cyanide by the harmless thiazolium salts as catalysts for benzoin condensation is a much safer and green alternative.

PROCEDURE
Approximately 1.3 g of thiamine hydrochloride was added to a 50ml Erlenmeyer flask. To this, 4 mL of water and 15 mL of 95% ethanol were added, and the solution was then cooled in an ice water bath. Then, 2.5 mL of 3M sodium hydroxide was added dropwise with swirling such that the temperature of the solution did not rise above 20C.To this yellowish solution 7.5 mL of pure benzaldehyde was added. This was stored in the laboratory until the following session. Instead of heating the reaction, the week period between sessions allowed for the condensation reaction to occur. At this time crystalline product was already formed. A suction filtration apparatus was assembled as seen in 3. The product was collected via suction filtration.

During collection the crystalline product was washed of its yellow color by a 1:1 mixture of 95% ethanol and water.

Table of Reactants & Products


Name Structure Mol. Wt. (g)
106.15

Amt Used
7.5 mL

Mol Used
0.05

Eq.

b.p/m.p (C)
178.1 -29

Density

BENZALDEHYDE

1.00

g/mL

THIAMINE HYDROCHLORIDE
Cl-

300.81

1.3 g

.025

2.00

NA 250 344 134-35

g/mL

BENZOIN

BENZOIN

212.24

1.31 g/cm3

Solubility data: Benzaldehyde: Soluble in this ethanol Soluble in acetone. Thiamine Hydrochloride: Soluble in water, methanol, and glycerol and practically insoluble in less polar organic solvents. Benzoin: slightly soluble in water, soluble in acetone

DATA & CALCULATIONS


ACTUAL YIELD: THEORETICAL YIELD: PERCENT YIELD: MELTING POINT:

4.1356

1.04 G 53 % TRIAL 1: 129 AVG: 130C TRIAL 2: 131C (SLIGHTLY WET SAMPLE)

OBSERVATIONS AND REMARKS


One notable observation made during the experiment was the yellow color that appeared after adding the reagents the Erlenmeyer flask. This yellow color could be related to the first step of the reaction, where the thiazolium salt is deprotonated, and the catalyst is generated. Lastly, the resulting product was crystals that were yellow in color. The low percent yield (52%) obtained in the experiment could be due to the fact that many of the crystals were stuck in the reaction tube and could not be removed for weighing. Lastly, the melting point of my sample could have been negatively affected through not giving the product a sufficient amount of time to dry.