Taylor, David

CHM 2211L

7/26/2018

Lab Report 5: Benzoin Synthesis

Introduction:

The purpose of this lab is to synthesize benzoin (C14H12O2) from benzaldehyde (C7H6O) via reflux,

crystallization, and filtration. Thiamine hydrochloride, which is similar to a physiologically common

coenzyme called thiamine pyrophosphate, will be used as a catalyst for this reaction. The thiamine HCL

will be converted to a ylide to allow for the catalysis of the benzoin synthesis; this is done with the help

of ethanol. Benzoin is commonly used in skin-care products to treat irritation and infection.1 The crude

product will be crystallized and recrystallized to ensure the purest possible benzoin will be obtained.

Furthermore, an IR spectrum and the melting point of the product will be determined testing the purity

of the product. Recrystallization is a process by which the initial crystals are further purified by getting

rid of any residual impurities left over from the first crystals by filtering them out utilizing vacuum

filtration. The vibration and rotation of the molecules that constitute the final product will dictate the IR

spectrum and because the spectrum of benzoin is already known, will determine the purity of the

benzoin. Similarly, a melting point determination also helps to determine the purity based on how

much it coincides with benzoin’s known MP.

Experimental Methods:

Thiamine hydrochloride (1.5 g,, 4.45 mmol) was dissolved in water (2 mL, 2 g, 0.000111 mmol). Ethanol

(15 mL, 11.78 g, 255.7 mmol) was added and the mixture was swirled until homogenized; aqueous

sodium hydroxide (4.5 mL, 9.59 g, 239.6 mmol) was added in and swirled until the color became pale
yellow. Pure benzaldehyde (4.5 mL, 4.68 g, 44.1 mmol) was added and a reflux apparatus was

assembled. The mixture was heated in the apparatus for 60 minutes. The mixture was then cooled to

room temperature. After crystallization the product was washed out of the flask with cold DI water two

times and placed in a funnel for vacuum filtration. The crystals were then paced back in a flask and

mixed with 8 mL of ethanol was mixed with the product for every gram of the product obtained and

mildly heated until the EtOH dissolved. When crystals were starting to form, the product was placed in

an ice bath until it was almost entirely crystallized. The product was again placed in a funnel for

recrystallization by being washed out with 5 mL of cold ethanol. The product was then weighed, the IR

spectrum taken after drying in an oven heated at 115o C, and the melting point determined; all were

recorded.

Results:

Theoretical Yield:

1 𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑚𝑜𝑙 𝑟𝑎𝑡𝑖𝑜 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑚𝑤 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 ∗ ∗ ∗ = weight of product
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑀𝑊 𝑚𝑜𝑙 𝑟𝑎𝑡𝑖𝑜 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 1 𝑚𝑜𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

1 𝑚𝑜𝑙 𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
4.68 𝑔 𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 ∗ = 0.00441 𝑚𝑜𝑙 𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
106.12 𝑔 𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒

0.00441 𝑚𝑜𝑙
= 0.002205 𝑚𝑜𝑙 𝐵𝑒𝑛𝑧𝑜𝑖𝑛
2

212.25 𝑔 𝐵𝑒𝑛𝑧𝑜𝑖𝑛
0.002205 𝑚𝑜𝑙 𝐵𝑒𝑛𝑧𝑜𝑖𝑛 ∗ = 4.68 𝑔 𝑏𝑒𝑛𝑧𝑜𝑖𝑛
𝑚𝑜𝑙 𝐵𝑒𝑛𝑧𝑜𝑖𝑛

Observed Yield:

Cork=30.03 g

Flask=92.11 g
Filter Paper=0.12 g

Crude Product=4.80 g-0.12 g=4.68 g crude product

Mass of Final Product=1.61 g

Percent Yield:

𝐴𝑐𝑡𝑢𝑎𝑙 𝑌𝑖𝑒𝑙𝑑 1.61 𝑔

𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑌𝑖𝑒𝑙𝑑
∗ 100% 4.68 𝑔
∗ 100% = 34.4%

Benzoin IR Spectrum:

Figure 1: Benzoin IR Spectrum (Experimental)

Significant Peaks (cm-1) Functional Group Type of Vibration Intensity

3400 H-Bonded Alcohol Medium

1677.03 Alkene Stretch Medium

753.43 Chloride Strong

694.75 Aromatic Out-of-Plane Bend Strong

594.58 Chloride Strong

510.99 Chloride Strong

Table 1: IR Spectrum Results

Expected IR Spectrum:

Figure 2: Benzoin IR Spectrum (Expected)2

Melting Point Determination:

Observed: 129-135o C

Expected: 134-135o C

Discussion and Conclusions:

Thiamine Hydrochloride, because of its structural similarity to thiamine pyrophosphate, works as a good

catalyst for the synthesis of benzoin from two benzaldehyde molecules due to the presence of a thiazole

ring. Once it is converted to a ylide with catalysis from a base (NaOH), it can react with benzaldehydes

to form benzoin. According to the results obtained in lab, the experiment was successful with the

exception of the percent yield. Qualitatively, the product resembled benzoin based on its known

properties, which is possessing an off-yellow hue; this color and texture came about after

recrystallization. Quantitatively, the results mostly coincided with what was expected. Everything but

the yield was very similar. The IR spectrum, aside from the inexplicable reverse peak seen around

3000 cm-1, possessed all the important peaks that constitute the spectrum of pure benzoin with minimal

deviation. All groups are represented by the IR spectrum. Similarly, the range of the melting point of

129-135o C fell within the parameter of the known melting point of 134-135o C rectifying that the

product most likely is benzoin with few impurities. The issue lied in the fact that the percent yield was

so low, but this could very well be due to human error. Perhaps not all crystals were removed from the

flask when washing them into the funnel for filtration. The issue in the IR spectrum was most likely due

to software error because it was a consistent problem for a short while, and that seems to be the only

possible explanation with everything considered. In summation, even with a product that is pure, all

methods of extracting it for testing must be done with considerable dexterity to ensure that all results
are as precise and accurate as possible; be careful when washing out the crystals, for some may be lost

or not noticed and forgotten.

Synthesis and Evaluation:

Thiamine hydrochloride

Figure 3: Benzoin synthesis via thiamine hydrochloride catalysis

The journal article discusses a more efficient way to synthesize benzoin utilizing different catalysts, while

also proceeding faster. The article discusses how using potassium cyanide (KCN) as a catalyst under

ultrasound radiation serves as a good catalyst to obtain benzoin. This is practical considering benzoin is

frequently used in skin-products to treat skin irritation, hence making it potentially more economically

practical to use KCN as a catalyst reducing production costs as well as increasing yield. This could

possibly having positive economic ramifications, costing the consumer and producer less; more people

will have access to necessary products and it will add to the economy. Environmentally it can potentially

be safer as well as more product is made much quicker saving on energy costs, hence using less energy.

The reaction time to crystallization takes only 10 minutes and there is a 90% yield obtained.

Furthermore it could be achieved at room temperature. Another method involved is an imidazolium

catalyzed method which holds a 97% yield in 5 minutes.3 All of this is under ultrasound irradiation

further catalyzing the reaction and recrystallization proceeds similar to how it is done in the lab

procedure, by washing it with EtOH. These methods are efficient and simple to do under the right

conditions and can prove beneficial. Conclusively these methods are economically and environmentally

viable and prove extremely practical and pave the way for new potential syntheses to be discovered.
 References

1
"BENZOIN - TOPICAL Side Effects, Medical Uses, and Drug Interactions." MedicineNet. MedicineNet, n.d.

Web. 28 July 2017.

2
"Benzoin." AIST:Spectral Database for Organic Compounds,SDBS. Spectral Database

For Organic Compounds SDBS, n.d. Web. 26 July 2017.

3Safari,
Javad, Zohre Zarnegar, Masoume Ahmadi, and Susan Seyyedi. "An Investigation of the

Catalytic Potential of Potassium Cyanide and Imidazolium Salts for Ultrasound-assisted

Synthesis of Benzoin Derivatives." Journal of Saudi Chemical Society 19.6 (2015): 628-33.

Web.