Vivian Saravanan

27 March 2018

Emily Smith

Benzoin Reduction via Sodium Borohydride

Purpose:

The purpose of this experiment was to reduce benzoin to 1,2-diphenylethane-1,2-diol using

sodium borohydride and to determine the effectiveness of this reduction using thin layer

chromatography.

Reaction Scheme:

Experimental Procedure:

To a 25 mL Erlenmeyer flask, 0.520 g of benzoin and 4 mL of ethanol were added. The flask

was gently heated on a sand bath and swirled until the benzoin crystals had dissolved completely.

0.1 g sodium borohydride was measured out onto a weighing paper and added in small portions

over the course of 5 minutes. The mixture was then swirled for 20 minutes as it gradually turned yellow
and then clear again. At the end of 20 minutes, the mixture-containing flask was placed into an ice bath,

and 5mL of distilled water was added along with 0.3 mL 6M hydrochloric acid.

After an additional 15 minutes, 2.5 mL more of distilled water were added. A white precipitate

had formed, which was filtered out using vacuum filtration, washed with 10 drops of ice-cold water,

and allowed to dry under vacuum for 15 minutes. The resulting solid, which still contained some

moisture, was massed and the melting point taken. About 2-5 milligrams of product was reserved for

thin-layer chromatography (TLC).

The remainder of the product was recrystallized with acetone and the mass and melting point of

the product taken again. This product was relatively pure due to the extra recrystallization step which

was suspected to have removed most of the remaining water in addition to other potential impurities.

In order to characterize the purity of the product, TLC was done on silicon dioxide plates. Two

TLC plates were labeled Plate 1 and Plate 2 prepared to accept three separate spots each, labeled A, B,

and C. Three separate solutions were prepared by dissolving ~1 mg each of the starting benzoin, the

crude product, and the final product in 1-2 mL of ethyl acetate.

On TLC Plate 1, A was spotted with two portions of benzoin solution, B was spotted with two

portions of crude product solution, and C was spotted with one part benzoin solution and one part crude

product solution.

On Plate 2, A was spotted with two portions of benzoin solution, B was spotted with two

portions of final product solution, and C was spotted with one part benzoin solution and one part final

product solution.

The plates were then developed in a 9:1 dichloromethane to ethanol eluent. The spots were

observed using ultraviolet radiation and marked in pencil; measurements to calculate Rf values were

taken.
Results:

Table 1. Yield

Benzoin Crude Product Recrystallized Theoretical Percent Yield

Product Value
Mass (g) 0.520 0.546 0.295 0.524
Melting point 132 131-135 137-138 -
-
(C)
- 56.3

Table 2. TLC spot designations and Rf values

TLC Spot Sample Identity Rf Value

1 2
Plate
A. Starting Material (Benzoin) 0.85 -
B. Crude Product 0.75 -
1
C. Starting Material + Crude Product 0.80 0.70
A. Staring Material (Benzoin) 0.82 -
B. Final Product 0.53 -
2
C. Starting Material + Final Product 0.82 0.53

Discussion:

The objective of this procedure was to reduce benzoin to 1,2-diphenylethane-1,2-diol with

sodium borohydride in an aprotic environment provided by ethanol and then work up the product with

hydrochloric acid into a precipitate that could then be separated from the reaction environment via

filtration.
 No direct characterisation of the product was conducted. However, the product was assumed to

be 1,2-diphenylethane-1,2-diol. The melting point of the crude product was 131-135 C, which was a

range 4 C, reflecting the crudeness of the product. The crude product weighed 0.546 g while the

starting material weighed only 0.520 g. The addition of one molar equivalent of hydrogen to the

starting benzoin could not account for all of this additional mass. It was suspected that the additional

mass was a result of excess water that had not been driven from the product. When the product was

recrystallized with acetone and the melting point taken again, it was 137-138 C, which was a range of 1

C. This reflected relative purity of the product.

The TLC characterisation of the product was sufficient to demonstrate a chemical difference

between the starting material (benzoin) and the final product, as final product had an Rf value 0.29

lower than the starting material. This is a significant difference, and demonstrates increased affinity of

the product to the silicon dioxide phase of the TLC plate which is suggestive of an increased capacity

for hydrogen bonding. As the expected product, 1,2-diphenylethane-1,2-diol has one more hydroxyl

functional group than the starting material, benzoin, the difference in Rf values supports the hypothesis

that the product is indeed 1,2-diphenylethane-1,2-diol.

It can be noted that the crude product’s Rf value was only 0.1 lower than that of the starting

material. This might be explained by the extra presence of water, which has a reputation for a high

capacity for hydrogen bonding with hydroxyl groups, obfuscating interaction between the hydroxyl

groups on the 1,2-diphenylethane-1,2-diol with the silicon dioxide of the plate. Of note is that the crude

product only produced one spot despite the melting point range of 4 C indicating a relatively impure

product. This might further suggest that the impurity present was a small amount of water hydrogen

bonded with the hydroxyl groups, increasing the degree of hydration of the sample without introducing

other distinct species.

 The theoretical yield, calculated using stoichiometric values, from 520 mg benzoin was 524 mg

of 1,2-diphenylethane-1,2-diol. The only chemical change was the addition of one molar equivalent of

hydrogen. 295 mg of final product were obtained, representing a 56 percent yield.