Nathan Lisbin

Synthetic FFR #1

Making Soap from Nutmeg

Introduction

Saponification is one of the oldest chemical reactions in practice, having records of

making soap from five thousand years ago.1 This chemical process is capable of hydrolyzing fats,

oils, and triglycerides into the fatty acid salts we use as soaps.1 The function of fatty acids salts as

a cleanser can be explained in its chemical structure as described by sodium myristate in Scheme

1. Since fatty acids salts contain a polar head and nonpolar hydrocarbon tail, in water the tails

will surround each other to reduce surface tension to decrease polar interactions forming a

micelle. In doing this the micelles also act an as cleanser surrounding unwanted exogenous

lipophilic material such as dirt and oils, so when the soap is washed off with water, so is the

unwanted material.2 However saponification has also been used heavily in industry as the

production of fatty acids can be derived from vegetable and animal oils and fats and also make

the valuable side product, glycerol. Glycerol is used in my biochemical reactions and has many

beneficial properties such as being used a sweetener making it in high demand.3 Also, besides

being precursors to soap, fatty acids can also be used as precursors to food, cosmetics, detergent,

and other products that related to peoples everyday lives.4

Due to the importance of saponification, in this experiment, Trimyristin, a triglyceride,

will be extracted from nutmeg and then hydrolyzed by sodium hydroxide to the fatty acid salt,

Sodium Myristate with Glycerol byproduct as shown in Figure 1 below.

Figure 1. Synthesis of Sodium Myristate from Trimyristin.

To initialize the reaction of Trimyristin into Sodium Myristate, the introduction of a

strong base and heat must occur. The reaction mechanism for this synthesis can be seen below

on Scheme 1. In this experiment, the addition of Sodium Hydroxide creates OH- ions in the

ethanol/Trimyristin solution which can then in conjunction with heat initiate the reaction loop.

The OH- ions are able to attack any of the three symmetrical nucleophilic carbons that are double

bonded with oxygen. This forms a tetrahedral intermediate in the Trimyristin complex where the

oxygen that was originally part of the C=O double bond now has unpaired electrons. To stabilize

itself the oxygens lone pair of electrons will recreate the double bond and pushing the charge to

the closest oxygen to the center of the molecule. This process breaks the ester bond holding the

complex together creating a Trimyristin intermediate and one Myristic acid. Then, the oxygen

with unpaired electrons on Trimyristin intermediate will deprotonate the Myristic acid. The

counter cation Na+ will then ionically bond with the negatively charged oxygen on Myristic acid

to form the desired product, Sodium Myristate. The OH- ions can then continue the reaction loop

two more times for each nucleophilic carbon double bonded to an oxygen making effectively

three Sodium Myristates for every Trimyristin consumed.

Scheme 1. Saponification mechanism of Trimyristin to Sodium Myristate by NaOH.

The overall purpose of this experiment was to synthesize Sodium Myristate by

saponification. This was done by first isolating Trimyristin from commercial ground nutmeg and

purified by recrystallization through ethanol. The purified Trimyristin was then saponified to
Sodium Myristate and also purified through recrystallization. The product was subject to

characterization by IR analysis.

Experimental

Trimyristin. Ground nutmeg (10g) and Diethyl ether (30 mL) were combined and refluxed for

30 minutes. Upon completion the excess ground nutmeg was removed by vacuum filtration and

washed with ether (2 x 20mL). The ether was evaporated to yield a light yellow crude product of

Trimyristin (3.44g, 4.757 mmol). The crude product was recrystallized 95% ethanol and vacuum

filtered to get the purified white solid product of Trimyristin (1.25g, 250% recovery). mp 55 C;

IR (ATR) ymax (cm1) 2912, 1731.

Sodium Myristate. 95% ethanol (4 mL), NaOH pellets (0.040g, 1 mmol), and Trimyristin (200

mg, 0.277 mmol) were combined and reluxed for 20 minutes. Upon completion, distilled water

(5 mL) and saturated NaCl (10 mL) was added to the solution and left to sit till a thick paste

product formed. The product was isolated through a vacuum filter and washed with cold water

(30 mL) to get the purified white solid of Sodium Myristate (0.6265g, 331.5% yield). IR (ATR)

ymax (cm1) 3270, 2919, 1743.

Results and Discussion

The synthesis of sodium myristate was done by saponification of the triglyceride

Trimyristin. The addition of a strong base allowed for the nucleophilic attack on the carbon

doubled bonded to oxygen and ultimately the breakdown of the Trimyristin molecule into three

sodium myristates and glycerol.

In the first part of this experiment, ground nutmeg was refluxed to isolate out Trimyristin.

From literature it is known that typically 5% of the mass used for nutmeg can be extracted as

Trimyristin. Using 10g of nutmeg, approximately 3.44g of crude Trimyristin was collected.
However, after a recrystallization using 95% ethanol was performed only 1.25g of dried

Trimyristin was isolated. This lead to the recrystallization percent yield being 36.3%. From

literature the recrystallization percent yield was around 24.3%1. The reason for the low

recrystallization percent yields is most likely due the difficulty in recrystallizing Trimyristin.

Since the melting point of Trimyristin is relatively low around 56-58 C, it was important to heat

the solution up slowly to dissolve the Trimyristin without oiling out the solid. The percent yield

using the purified sample of Trimyristin was 250%. This unrealistic percent yield was probably

caused by small amounts of solution still being inside the solid product. To prove that

Trimyristin was synthesized first a melting test was done on the sample. As mentioned earlier,

from literature it is known that the melting point range of Trimyristin is 56-58 C.1

Experimentally it was found to be 55 C which is very indicative of proving that Trimyristin was

synthesized. To further examine this product an IR analysis was ran of the sample product. The

IR spectrum can be seen in the Spectral Data (Figures 1 and 2, Supplemental Data). From the

data the most notable peaks of the IR spectrum occurred at 2912, 1731, and 1172 cm-1. The peak

at 2912 cm-1 represents the hydrocarbon bonds of the triglyceride tails. At 1731 cm-1 the peak

represents the three carbon oxygen double bonds that form the ester carbonyl groups. Finally,

the peak at 1127 cm-1 represent the carbon oxygen ester bond in Trimyristin. This data describes

Trimyristins molecular structure and was used for comparison to prove that Sodium Myristate

was made.

In the second part of the experiment, Saponification was done on Trimyristin under reflux

conditions to make Sodium Myristate. The overall yield after purification by vacuum filtration

and evaporation was 332%. It is reported that this experiment often leads to yields well over

100% even though theoretically it is impossible.1 The most logical explanation for this high yield
is that the product still has solvent such as water inside that was not able to evaporate out

increasing the weight significantly. To prove that Sodium Myristate was made and IR analysis

was taken of the sample. The IR spectrum can be seen in the Spectral Data (Figures 1 and 2,

Supplemental Data). The most notable peaks of the spectrum occurred at 3270, 2919, and 1742

cm-1. A very important peak in the spectrum at 3270 cm-1 is indicative of an oxygen hydrogen

bond. In Sodium Myristate alone there is no oxygen hydrogen bond as oxygen ionically attaches

to sodium. However, if water is present H+ of water could bond to the oxygen in place of sodium

producing this spectra peak. This would also help prove that solvent is still present inside the

sodium myristate sample. If solvent wasnt present, then no peak would have appeared.

However, this only holds true if the sample is Sodium Myristate as additional solvent inside a

sample of Trimyristin would not produce an oxygen hydrogen bond. Another peak occurs at

2919 cm-1 which similarly to Trimyristin refers to the hydrogen carbon bonds in the tail region of

Sodium Myristate. Lastly, the peak at 1742 cm-1 refers to the carbon oxygen double bond of the

carboxylic acid group. This peak is also indicative that the product synthesized is sodium

myristate. Since this carbon oxygen double bond is part of a carboxylic acid group it is a little

higher in wavenumber than an ester carbon oxygen double bond like the one present in

Trimyristin. Another notable difference is that there is no peak around 1100 cm-1 for Sodium

Myristate like there were was in Trimyristin. This peak was also representative of a carbon

oxygen ester bond which is only present in Trimyristin. The lack of this peak further indicates

that this product was not contaminated in any significant amount and that Sodium Myristate was

synthesized.

After analysis, a few tests were done of the sample of Sodium Myristate. The sample

was dissolved in water and separated into two different test tubes where olive oil and 1% FeCl3
were added separately. The addition of olive oil to the Sodium Myristate solution caused the oil

to mix with the solution. Since oil is essentially a lipid it should be able to form a mixture with

the Sodium Myristate solution which also contains lipid like features with the hydrocarbon tail.

Upon the addition of 1% FeCl3 the solution had a grey precipitate form. This was most likely

formed from the Fe3+ ion replacing the Na+ ion that is usually associated with Sodium Myristate

creating an insoluble solid in the test tube. This test is another proof that Sodium Myristate was

synthesized as Trimyristin would have no reactions involved with 1% FeCl3 that would result in

a precipitate.

The saponification of triglycerides, fats, and oils are a very focused area in organic

chemistry and industry as it is can be the basis for many products used in everyday life. The

overall saponification of Trimyristin to Sodium Myristate was successful having a percent yield

of 332%. As discussed earlier the unrealistic yield is usually over 100% due to solvent such as

water being trapped inside the product which was proven with the IR spectrum of Sodium

Myristate. In the future, better results for percent yield of the product could be taken if more

time was allowed for the products to dry between experiments. It is also possible that the

recrystallization could have had better yield if possibly a better solvent was used. Although

ethanol was a good solvent it may have still been too different in polarity to Myristate and cause

a less then optimal recrystallization compared to another solvent. Overall the products were

synthesized in explainable yields and produced data that supported their structures.
References
1
Mattos, M. C. S. D.; Nicodem, D. E. Soap From Nutmeg: An Integrated Introductory Organic

Chemistry Laboratory Experiment. J. Chem. Educ. Journal of Chemical Education. 2002, 79,

9496.
2
Walters, R. M.; Mao, G.; Gunn, E. T.; Hornby, S. Cleansing Formulations That Respect Skin

Barrier Integrity. Dermatology Research and Practice. 2012, 2012, 19.

3
Tan, H.; Aziz, A. A.; Aroua, M. Glycerol Production and Its Applications as a Raw Material: A

Review. Renewable and Sustainable Energy Reviews. 2013, 27, 118127.

4
Jumat Salimon, Bashar Mudhaffar Abdullah, and Nadia Salih, Saponification of Jatropha

curcas Seed Oil: Optimization by D-Optimal Design, International Journal of Chemical

Engineering, vol. 2012, Article ID 574780, 6 pages, 2012. doi:10.1155/2012/574780