Benjamin Sepe, Chem 213 Synthetic #4 FFR Making Soap from Nutmeg Introduction Soap is an essential compound in todays

society. Dating back thousands of years to its crude synthesis from animal fats mixed with basic salts; the multifaceted cleanser has since exploded into seemingly every trade.1 Its functions as a detergent range from the industrial application of alkyl polyethoxylates in paper, textile, and spermicide production to the world of medicine, where they are used in vaccines and disease treatment.2, 3 The average person, however, most likely interacts with soap as a personal hygiene tool or in the act of cleansing fabrics. Soap is known as an amphipathic molecule, meaning that it consists of two regions that differ in polarity.4 This difference in polarity is a result of the molecules long hydrophobic alkane tail and ionic head that is, in turn, hydrophilic.4 These differing polarities are the root of soaps unique ability to removing grease and oils from solution. As depicted in Figure 1, soap molecules readily form what are referred to as micelles in aqueous solution.5 These micelles often spawn around oil and grease due to the hydrophobic tail of a soap molecule readily dissolving in hydrophobic grease.4 The hydrophilic head remains at the surface of the micelle, however, at it is attracted to the polarity of surrounding water. 4 Thus, when the soapy solution is rinsed away, the micelle will wash away too, taking the grease with it and leaving the fabric or dish unsoiled.

Figure 1. A Soap Micelle.5 Soap molecules are synthesized by a mechanism called saponification. The mechanism of saponification in basic solution is characterized by the SN2 attack of a hydroxide group on an esters carbonyl group, resulting in an electron pushing mechanism that cleaves the ester bond. This yields a carboxylic acid that is quickly deprotonated by the removed alkoxide, yielding an enolate and an alcohol. The negative enolate ion is quenched, in most cases, by the positive sodium ion of sodium hydroxide. This general mechanism is depicted in Scheme 1.6

Scheme 1. Saponification: General Mechanism6 In naturally occurring fatty oils, the mentioned esters are usually found in groups of three, referred to as triglycerides. The triglyceride that is used in this lab is trimyristin. The synthesis calls for three equivalents of sodium hydroxide, and

each molecule of trimyristin yields three molecules of the soap sodium myristate and one equivalent of glycerol. The complete electron pushing mechanism for the synthesis of sodium myristate from trimyristin is depicted below in Scheme 2.

Scheme 2. Electron Pushing Diagram for Synthesis of Sodium Myristate from Trimyristin In this lab, the fatty oil trimyristin is extracted from ground nutmeg. Saponification of trimyristin yields sodium myristate and glycerol. The extraction of a fatty oil and successive saponification has been repeated time after time for the last 5 millennia as a way of producing some of the most versatile compounds known to man. In this lab, trimyristin and the soap sodium myristate may be analyzed by melting point and IR analysis to provide evidence that this synthesis was after all those years, once again, successful.

Experimental Trimyristin. Nutmeg (5.008 g) and diethyl ether (12.5 mL) were added to a 100 mL flask, refluxed for 30 minutes, then cooled to room temperature. Vacuum filtration removed residual Nutmeg from the product. Drying provided crude trimyristin as a yellow solid. Crude trimyristin was recrystallized in 95% ethanol at 50 OC. Vacuum filtration afforded pure trimyristin as a white powder (0.333 g, 6.65%) mp 52 54
OC;

IR (ATR) max (cm-1) 2954.8, 2915.4, 2849.2, 1732.3, 1175.7.

Sodium Myristate. 95% Ethanol (4 mL) and NaOH pellets (0.0425 g) were added to a 50 mL flask and stirred until homogeneous. The solution was combined with trimyristin (0.2013 g) and refluxed for 15 minutes. To the product, distilled water (4 mL) and saturated NaCl solution (8 mL) were added. Vacuum filtration afforded Sodium Myristate as a white powder (0.2933 g, 153.8 %); IR (ATR) max (cm-1) 2919.7, 2847.2, 1556.6, 1461.4, 1445.5, 1421.3, 722.1, 697.4.

Discussion and Conclusions The extraction of trimyristin from ground nutmeg utilized reflux in diethyl ether. The product of this reflux is depicted in Figure 2, below. The result of this reflux was a separated ether layer that contained trimyristin. After vacuum filtering out the residual nutmeg and extracting any remaining trimyristin with additional ether, the product was a thick yellow liquid, depicted in Figure 3.

Figure 2. Reflux Result

Figure 3. Crude Trimyristin (Wet)

The crude trimyristin solution was given time to dry as diethyl ether evaporated and afforded a solid crude trimyristin, depicted on the next page in Figure 4. In order to purify the crude trimyristin, it was necessary to recrystallize the solid in 95% ethanol, however due to the relatively low melting point of trimyristin (lit. 56- 57 0C) extra precaution was taken to be sure ethanol did not exceed this temperature. After recrystallization, trimyristin was evaluated for purity

by means of Thin Layer Chromatography. The Rf value (lit. 0.5) was matched identically by the product. The TLC plate, run in an iodine chamber is seen below in Figure 5.

Figure 4. Crude Trimyristin Solid

Figure 5. TLC Analysis Pure

IR analysis of the recrystallized trimyristin provided evidence that the product had formed according to plan. In the IR spectrum, provided as supplementary Figure 6, a strong group of peaks in indicated around 2914 cm-1. These peaks represent the numerous C-H bonds in the long hydrophobic alkane chains. Additionally, a large singular peak at 1732.3 cm-1 was indicative of the ester C=O groups. The esters were again represented as a large peak at 1175 cm-1, signifying the C-O bonds. Melting point determination also provided insight into the analysis of this compound. The observed melting point range of 52 54 0C was very close to the

literature value of 56-57 0C, representative of a highly pure substance. The percent recovery from nutmeg, furthermore, was calculated to be 6.65%. Saponification of the trimyristin compound was carried out by refluxing the fatty triglyceride with NaOH pellets in 95% ethanol. After workup, the product resembled a chalky white powder, depicted below as Figure 7.

Figure 7. Sodium Myristate Melting point analysis provided evidence as to successful soap salt formation, as the product reached capacity of the Mel-Temp machine without successfully turning into a liquid. This behavior is characteristic of these salt soaps. Additionally, IR analysis of the compound, supplementary Figure 8, provided evidence of successful saponification. The peaks at 2919 cm-1, similarly to trimyristin, were

representative of the C-H bonds in the long saturated alkane chain. Additionally, the peaks at 1556.6 cm-1 were indicative of the ester bond formed by the salt soap. Finally, it is important to note that the small alcohol bump at around 3200 cm-1 was generated by the small amount of product that formed a carboxylic acid in solution. The product was in larger than expected yield at 153.8%. One possible reason for this anomaly could be differences in the scales in our laboratory. With any two scales differing by as much as 30 milligrams, it is more likely than not that taking an initial measurement at a scale that under-measured my reagent and taking a final measurement on a scale that over-measured my product. In the future, more attention should be paid to the specific scale being used. This scale should be kept constant throughout the experiment to keep at least relative consistency. The final analysis that was conducted on the synthesized sodium myristate was a set of tests including sodium myristate solution, vegetable oil, and 1% FeCl3. A solution of 0.01 g sodium myristate: 1 mL of water was made in excess. To two reaction tubes, 5 mL of the solution was added. In Tube A, vegetable oil was added. The effect was dissolution of additional sodium myristate, indicative of the way that you would expect soap to dissolve oil. In Tube B, %1 FeCl3 was added. The result was a precipitate forming, likely a salt (NaCl), indicative of the inability of this compound to dissolve in the soap water. The results are summarized in Figure 9. TUBE A: Sodium Myristate + Veg. Oil Veg. Oil was dissolved TUBE B: Sodium Myristate + FeCl3 Precipitate formed, likely NaCl

Figure 9. Results of Chemical Analysis

Given the results of this experiment, it is with reasonable confidence that the appropriate compound, sodium myristate, was isolated. Using saponification, it was proven possible to take extracted oils and create a soap product. It is important to take away from this lab the significance of detergents in everyday life. Their applications are numerous, and processes much like those in this lab are happening every day to make our world a better, and cleaner, place.

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