Assignment No.

1 Material chemistry (CH-527)

Monoglyceride Stearate Synthesis

Submitted to Dr. Sohail Nadeem

Submitted by Mehwish Jameel (14003140023)
4th Semester

School of Sciences
Department of Chemistry
University of Management & Technology Lahore

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 Assignment No.1 Material chemistry (CH-527)

Introduction
Glycerides:
Glycerol esters are the largest group of fatty acid partial esters of commercial significance. Due
to the presence of specific hydrophilic and hydrophobic moieties in their structures, they act as
important non-ionic surfactants of low HLB value, especially valuable as benign and
environmentally friendly ‘‘water in oil’’ emulsifiers.

Glycerol Mono Glyceride di Glyceride tri Glyceride

Monoglyceride stearate:
Monoglyceride is a glyceride in which each glycerol molecule has formed an ester bond with
exactly one fatty acid molecule. The more formally correct terms in modern convention are
acylglycerol and monoacylglycerol.
Monoacylglycerols are variously produced by biological or industrial chemical processes.
Biochemically they commonly are formed by enzymatic hydrolysis of triglycerides by the action
of lipoprotein lipase, by enzymatic hydrolysis of a fatty acid from diacylglycerol by the action of
diacylglycerol lipase, or as an intermediate in the alkanoylation of glycerol to form fats.
Glycerides (also known as acylglycerols) are esterified to glycerol with fatty acids. Glycerol
having three hydroxyl functional groups is esterified with one, two or three fatty acids to form
monoglycerides, diglycerides and triglycerides respectively. A monoglycerides is a compound
consisting of one fatty acid chains covalently bonded to a glycerol molecule through ester
linkage
The commercial source may be either animal or vegetable fats, and synthetically produced as
well. Mono- and diglycerides are common food additives used as an emulsifier or stabilizer to
blend together certain ingredients of oil-hating and water-hating, which would not otherwise
blend well.

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 Assignment No.1 Material chemistry (CH-527)

Glycerol stearate is a natural fatty compound often used as an emulsifier, emulsion stabilizer,
emollient, moisturizer and viscosity builder in creams and lotions. It is also used as an opacifying
and pearlizing agent in cosmetics. Glycerol stearate can be of plant origin (corn-based), animal
source or synthetic and is considered to be biodegradable, practically non-toxic orally and causes
no skin and minimal eye irritation. It is dispersible in water and is also soluble in oil and alcohol,
making it an ideal ingredient for cosmetics.
In a clinical trial with over 1,200 patients with eczema, glycerol monostearate was found to
produce absolutely no adverse reactions in a test of common emulsifiers (all other emulsifiers
tested did cause adverse reactions in a significant percentage of patients). It is used to keep
bakery goods fresh, improve flour quality, and as an emulsifying and whopping agent for ready-
to-eat products. It is also used in ice cream formulations, starch products, milk products, chewing
gum, chocolates and other foods.
It also serves as a softer in textiles and as an external lubricant for plastics. It provides the
functional characteristics of glycerol stearate and enhanced properties such as improved
emulsion stability, bodying and thickening properties and greater dispersability of colorants and
active materials. Semi-synthetic forms of glycerol stearate often use stearic acid isolated from
palm oil as a starting material, another waxy fatty acid widely used in cosmetics and soap.
Chemistry:

Glyceryl Monostearate
 Glycerol stearate is a fatty compound (C 17H35COO) 3C3H5). The formula for the
hydrocarbon radical (R) in the fat glycerol stearate is C 17H35. Glycerol stearate has a
melting point of 58°C, an acid value of 15, and an iodine value of 1.5. Fats are
technically described as esters of fatty acids and glycerol (soaps are metallic salts of fatty
acids).
 The reaction of glycerol stearate with sodium hydroxide to produce the soap sodium
stearate has the following chemical equation: C 17H35COO) 3C3H5 + 3NaOH -> C3H5 (OH)
3 + 3 C17H35COONa.

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 Assignment No.1 Material chemistry (CH-527)

 Glycerol monostearate has an acid value of 2% and a maximum iodine value of 5. It is

classified as an anionic modified emulsifier recommended for use in oil or water
emulsions that are in the pH range of 5 – 9, monoglyceride content between 42-45%,
maximum free glycerine content of 10% and water content of 1.5%. Mono- and
diglycerides of fatty acids (glyceryl monostearate, glyceryl distearate) are a normal part
of digestion, prepared commercially from glycerine and fatty acids. These are normally
obtained from hydrogenated soya bean oil so may be GMP grade.

Literature review for the synthesis of monoglycerides

stearate
Monoglycerides stearate have traditionally been prepared by catalytic glycerolysis of fats and oil
or fatty acid methyl esters. Direct esterification of glycerol with fatty acids in the presence of
homogeneous or heterogeneous catalysts have also been carried out the detailed process has been
discussed below:
Thengumpillil, et al., (2011) has found that the stearic acid and glycerol were reacted in a ratio
of 1:3 in presence of lactic acid (50% of total wt. of fatty acid and glycerol) at 140-150 o C for 5
hours. After the reaction mixture was cooled, dissolved in diethyl ether and washed with water to
remove unreacted glycerol and lactic acid. The solvent was removed under reduced pressure, the
product dried under vacuum and was analyzed by GC as trimethylsilyl derivative to determine
the individual composition of fatty acid, monoglycerides, diglyceride, and triglyceride in the
product.
The composition obtained as (FA, 37%; MG, 26%; DG, 14%; TG, 4%; LMG, 20%), the product
obtained in a good yield. The conversion of fatty acid was found to be 63% and selectivity of
monoglyceride over diglyceride was found to be 65%.
The main advantages of the reaction
1. It is a catalyst free process for the preparation of monoglycerides by esterification between
fatty acids and glycerol.
2. The reaction is carried out with the solvents which are completely safe, non-toxic and
biodegradable.
3. As no catalyst is used, there is no generation of aqueous effluents as in the case of
homogeneous catalysts. Hence the process is more environmentally friendly.

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 Assignment No.1 Material chemistry (CH-527)

4. The reaction is carried out at relatively milder conditions than earlier reported methods.
5. The presence of minor concentrations of lactylated monoglycerides may provide a
functionally superior product than glycerides alone
Yu, et al., (2003) evaluated the usual procedure for the preparation of the so called
monoglycerides as:
 The preparation of glyceryl monostearrite Glyceryl stearate as prepared in known manher
by heating glycerol with stearic acid and containing 35% oil the mono-ester, along with
the di and tri-esters, was dissolved in a mixture of tertiary butyl alcohol(200 g.) and
hexane (4-0 g.) To this solution, after drying by distillation, .was added potassium
hydroxide (1.0 g.) in glycerol (60 g.) from which the free water and the water of reaction
has been removed by distillation under vacuum. The weight of dry potassium glyceride
solution added was 47.6.g. The mixed solution was slowly stirred.
 At room temperature for three days during which the initially formed amorphous
precipitate gradually crystallized to pure mono-ester. The increased proportion of
glycerol caused by the precipitation and crystallization results in a redistribution of esters
in the mother continued for about one to three days. During this period the glyceryl
monostearate crystallizes from the solution and the conversion of the glyceryl stearate to
the mono-ester reaches a maximum of about 84-86% as determined by the periodate
method of analysis.
 The catalyst is neutralized by the addition of the calculated quantity of finely ground
citric acid to give a pH of 4.0 when water is added, and in this way the catalyst is
neutralized without causing hydrolysis of the ester. Distilled water is added next in an
amount equal to half the volume of the reaction mixture and the pH of the aqueous layer
is adjusted, if necessary to 4.0. The aqueous glycerol solution separates readily, but if any
difficulty is experienced the mixture is warmed to about liquor and it will also be
apparent that the concentration.
a. Protection of glycerol with acetone
A mixture of acetone (36 g), CHCl 3 (156 g), glycerol (30 g) and p-toluene sulfonic acid (1.2 g)
was refluxed for 6 h. Water formed during the reaction was removed continuously by Dean-Stark
apparatus. After cooling the reaction mixture, Na 2CO3 (1.3 g) was added and stirred for 30 min.

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 Assignment No.1 Material chemistry (CH-527)

The reaction mixture was vacuum distilled (10 mmHg) to obtain pure 1, 2-O-isopropyl-idene
glycerol.
b. Trans esterification
A mixture of methyl stearate (43 g, 0.15 mole) and 1, 2-O-isopropylidene glycerol (5) (30 g,
0.23mole) was stirred at 140 °C in the presence of Na 2CO3 (0 g) for 6 h. Methanol formed during
the reaction was removed continuously by evaporation under atmosphere. After the reaction was
completed, excess of 1,2-O-isopropylidene glycerol was recovered under vacuum (10 mmHg)
and the residue was dissolved in ether, washed with water to remove Na 2CO3 and concentrated to
give 1,2-O-isopropylideneglycerol stearate (6) (56 g, 97%) which was used in the next step
without further purification.

+
Glycerol Fatty acid Mono Glyceride
c. DE protection
Compound 6(10 g) in ethanol (95%, 40mL) was refluxed for 3 h in the presence of Amberlyst
15(wet) ion-exchange resin (1.0 g). The reaction mixture was filtered and the filtrate was
concentrated to give GMS (1) (8.8 g, 99% yield, 97% purity).

+
1, 2-O-isopropylidene glycerol Ester 1, 2-O-isopropylidene glyceride
When we studied the transesterification of 5 into 6 using a basic catalyst, which is followed by
the efficient deprotection to obtain highly pure GMS.1

Na2CO3
Glycerol 1, 2-O-isopropylidene glycerol

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 Assignment No.1 Material chemistry (CH-527)

EtOH, Acid Resin

Monoglycerides stearate 1, 2-O-isopropylidene glyceride stearate
Bancquart, et al., (2001) stated that the preparation of monoglycerides from fatty acids or fatty
methyl esters and glycerol can be carried out in the presence of acid or basic catalysts. The use of
solid basic catalysts could limit secondary reactions leading to product degradation. A
comparison of several basic solids (MgO, CeO 2, La2O3 and ZnO) has shown that the more
significant the intrinsic basicity is, the more active the catalyst is. In order to increase the
performance of these solids, several methods have been used for the preparation of MgO and
CeO2. MgO prepared by hydration followed by calcination of a commercial raw material is the
most active catalyst.2
Bloomer, et al., (1992) reported that the facile synthesis of esters by lipase-catalyzed esterification
of fatty acids and ethanol is demonstrated. Evaporation of the water generated in the reaction
allowed the rapid production of esters of >99% yield in refluxing pentane or hexane. Water was
trapped by condensing the refluxing vapor phase and passing it over activated molecular sieves
in a reflux trap. High yields were rapidly obtained in synthesis of ethyl esters of oleic, linoleic, α-
linoleic, and arachidonic acids without peroxidation of double bonds. The wax ester oleyl oleate
was also synthesized rapidly with little peroxidation. A molar excess of 1.25 to 1.5 of ethanol
allowed the most rapid ester synthesis. Synthesis of ethyl stearate was carried out on a
preparative scale (50g). Greater than 99% conversion was obtained in 50 min.3
Ghand, et al, (2007) Highly pure a-monoglycerides (5a–e) were successfully prepared in high
yields by the condensation of fatty acids such as lauric, myristic, palmitic, stearic andoleic (2a–e)
with glycerol carbonate (4-hydroxymethyl-1,3-dioxolan-2-one) (1) in the presence of
triethylamine as catalyst. Solid Brönsted base catalysts show higher activity and much higher
specific rate than reported Lewis basic hydrotalcite catalyst for transesterification of oleic acid
methyl ester with glycerol. The selectivity of the former for monoglycerides is higher because of
the lower deactivation of the catalyst, which allows the transesterification of diglycerides to
occur at longer reaction times.4

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 Assignment No.1 Material chemistry (CH-527)

Corma, et al, (2005) Calcined Li–Al hydrotalcites give higher activity than MgO or Al–Mg
hydrotalcites because of the stronger Lewis basicity of the former. All of the solid Lewis basic
catalysts have the same selectivity to monoglyceride regardless of the base strength, a selectivity
lower than that of Brönsted basic solid catalysts.5
Conclusion:
There are different methods for the synthesis of esters of monoglycerides stearate has been employed
depending upon cost factor pH stability, acid and base balance catalyst depending upon the reaction
scheme and all of are equal importance. The best yield is obtained through Chemical method is important
because our product is obtained through routes that require by products from other synthesis.

References

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1
Yu, C. C., Lee, Y. S., Cheon, B. S., & Lee, S. H. (2003). Synthesis of Glycerol Monostearate with
High Purity. Bulletin of the Korean Chemical Society, 24(8), 1229-1231.
2
Bancquart, S., Vanhove, C., Pouilloux, Y., & Barrault, J. (2001). Glycerol transesterification with
methyl stearate over solid basic catalysts: I. Relationship between activity and basicity. Applied
Catalysis A: General, 218(1), 1-11.
3
Bloomer, S., Adlercreutz, P., & Mattiasson, B. (1992). Facile synthesis of fatty acid esters in high yields.
Enzyme and microbial technology, 14(7), 546-552.
4
Ghandi, M., Mostashari, A., Karegar, M., & Barzegar, M. (2007). Efficient synthesis of α-monoglycerides via
solventless condensation of fatty acids with glycerol carbonate. Journal of the American Oil Chemists' Society,
84(7), 681-685.
5
Corma, A., Hamid, S. B. A., Iborra, S., & Velty, A. (2005). Lewis and Brönsted basic active sites on solid
catalysts and their role in the synthesis of monoglycerides. Journal of Catalysis, 234(2), 340-347.