preparation and properties of fully esterified erythritol

Research Article

Preparation and properties of fully esterified erythritol

Panayiotis V. Ioannou, Maria A. Lala and Gerasimos M. Tsivgoulis

Department of Chemistry, University of Patras, Patras, Greece

Pure tetraesters of erythritol with C10, C12, C14, C16, C18 saturated, and C18:1 unsaturated (oleoyl) fatty

acyl chains have been prepared for the first time and characterized using the acylating systems fatty acid/

N,N0-dicyclohexylcarbodiimide/4-dimethylaminopyridine (DMAP), fatty acid anhydride/DMAP, fatty

acyl chloride/pyridine, and fatty acyl chloride/boron trifluoride etherate. For the first three systems the

yields were in the range of 80–90% while the fatty acyl chloride/pyridine system has the advantage of

lower cost. The fatty acyl chloride/boron trifluoride etherate system gave lower (ca 70%) yields of the

tetraesters. The tetraesters of erythritol may have applications analogues to those of triglycerides. In

addition, new applications can be envisaged for these compounds, as a result of their differences in

physical, chemical, and biochemical properties compared to triglycerides.

Practical applications: The tetraesters of erythritol with saturated fatty acyl chains may have appli-

cations analogous to those of saturated triglycerides. However, tetraesters with unsaturated fatty acid

chains may have greater prospects of having industrial uses after doing chemistry on the carbon–carbon

double bonds.

Keywords: Acylations / Erythritol / Fatty acid anhydrides / Fatty acyl chlorides

Received: October 20, 2010 / Revised: February 15, 2011 / Accepted: June 1, 2011

DOI: 10.1002/ejlt.201000508

: Supporting information available online

1 Introduction

Simple triglycerides, e.g., tristearin, tripalmitin, etc., are well

known esters of glycerol of animal and vegetable origin [1]

having interesting physicochemical and biochemical proper-

ties [2]. Unsaturated triglycerides of plant origin can be

manipulated, after their isolation and purification, to give

useful products, e.g., polymeric materials [3].

From the tetritols, meso-erythritol and D- and L-threitols,

erythritol occurs widely in nature, e.g., in foods, microorgan-

isms, animals, and humans, although in very small amounts.

It can be produced from corn or wheat starch via fermenta-

tion of the enzymatic hydrolysis of glucose by microorgan-

isms, and it is not toxic for human use, e.g., as a low calorie

sweetener [4].

It is of interest that only two tetraesters of erythritol are

known in pure state: the tetrabenzoate, prepared from eryth-

ritol and benzoyl chloride (1:5 mole ratio) in pyridine, m.p.

1888C [5] and the tetraacetate, prepared from erythritol

tetranitrate, acetic anhydride, and 100% sulfuric acid, m.p.

86–888C [6]. Usually, the simple tetraesters of erythritol

were obtained as mixtures when erythritol reacted with

palmitoyl or stearoyl chlorides using different mole

ratios [7]. At 200–2508C, erythritol and palmitic acid under

various mole ratios again gave mixtures containing differing

proportions of tetrapalmitate [7]. The reactions of

decanoic (capric), dodecanoic (lauric), tetradecanoic

(myristic), hexadecanoic (palmitic), and octadecanoic (stea-

ric) acids with erythritol under 1:1.25 mole ratio at 1608C/

440 Torr to 2008C/20 Torr gave (by TLC analysis) all nine

positional isomers of mono-, di-, tri-, and tetra-esters of

erythritol as well as esters of cis and trans 3,4-dihydroxyte-

trahydrofuran [8].

Correspondence: Prof. Panayiotis V. Ioannou, Department of Chemistry,

University of Patras, Patras, Greece

E-mail: [email protected]

Fax: þ30 2610 997118

Abbreviations: DCC, N,N0-dicyclohexylcarbodiimide; DHU, 1,3-

dicyclohexylurea; DMAP, 4-dimethylaminopyridine; py, pyridine; peth,

petroleum ether; RCOCl, fatty acyl chloride; RCOOH, fatty acid;

(RCO)2O, fatty acid anhydride

Eur. J. Lipid Sci. Technol. 2011, 113, 1357–1362 1357

� 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com

The tetraesters of pentaerythritol were prepared by heat-

ing pentaerythritol and fatty acids (1:8 mole ratio) at 1808Cfor 40 h [9].

Approaching the insolubility problem of erythritol in all

common organic solvents from a practical (i.e., cost) and

scientific (i.e., yields and purity) point of view, we note that

the esterification, RCOOH þ R0OH > RCOOR0 þ H2O,

even when the reactants are in one phase is a slow reaction

and reaches equilibrium. However, activation of the acid or

the alcohol can accelerate this reaction. For example, acti-

vation of the carboxylic acid so that it can undergo a faster

nucleophilic attack on the carbonyl group [10] can be done by

protonation [11].

On the other hand, the yields of the final esters can be

increased by removing the water or by using excess of the

alcohol. Also, higher yields have been obtained by conversion

of the acid to an acyl chloride which can be further activated

by pyridine or Et3N or 4-dimethylaminopyridine (DMAP)

[12, 13], or conversion of the acid to its anhydride which can

further be activated by, especially, DMAP [12, 13].

However, in the anhydride procedure, half of the acid is

wasted. In order to alleviate this drawback, researchers,

notably Khorana, introduced the acylation with the free

fatty acid in the presence of DCC which activates the

carboxylic acid but not the alcohol [14]. In spite of this, this

reaction as well has the drawback that N-acylureas are also

[15] or exclusively [16] obtained. Suppression of the

N-acylurea formation was achieved by using DMAP as a

catalyst [17] or 4-(dimethylamino)pyridinium 4-toluenesul-

fonate [18]. There are other, less frequently used, esterifica-

tion methods, e.g., conversion of the acid to mixed (organic–

inorganic) anhydride or to 2-acyloxy-1-methylpyridinium

salts [10].

Alternatively, esterification yields can be increased by

replacing the alcohol, e.g., with an alkyl halide R0X(which then suffers nucleophilic attack by the carboxyl or

carboxylate group [10]) or with the R0O-PPh3þ derivative

(the Mitsunobu reaction [19, 20]) but the last reaction is not

applicable to polyols having vicinal –OH groups [21].

31

OCOR

OCOR

RCOO

RCOO

2

RCOO

RCOO

RCOORCOO

RCOO OCOR

OCOR

In this paper we report on the preparation of meso-eryth-

ritol tetraesters 1 using four acylating systems: RCOOH/DCC

(N,N0-dicyclohexylcarbodiimide)/DMAP, (RCO)2O/DMAP,

RCOCl/py, and RCOCl/BF3 � Et2O, as well as a glycerol

triester 2 and pentaerythritol tetraesters 3 for evaluation of

the acylation times and yields. The tetraoleoyl ester 1was also

prepared and some experiments were done on the double

bonds.

2 Materials and methods

2.1 Materials

meso-Erythritol (Aldrich) was finely ground in an agate mor-

tar and then dried in vacuum over phosphorus pentoxide.

Pentaerythritol was from Fluka, boron trifluoride etherate,

dry glycerol, DMAP, and saturated fatty acid chlorides were

from Aldrich and were used as received. Oleoyl chloride

(Merck) was redistilled (colorless oil, b.p. 150–1558C/

0.35 mmHg). The fatty acid anhydrides were prepared from

fatty acids and DCC (Aldrich) according to Lapidot et al.

[22], they were pure by IR [23] and used without recrystal-

lization. Silica gel 60H for TLC and silica gel 60 for column

chromatography were from Merck. Dichloromethane, dime-

thylformamide, and redistilled pyridine were kept over A4

molecular sieves. The other solvents were of Analytical grade.

2.2 Methods

TLCs were run on microslides and the spots were made

visible by spraying with 35% sulfuric acid and charring. IR

spectra were taken in KBr disks on a Perkin-Elmer, model

16PC FT-IR spectrometer, while 1H NMR (at 400 MHz)

and 13C NMR (at 100 MHz) spectra were obtained on a

Bruker, model DPX Avance, spectrometer. Elemental

analyses were done by the Centre of Instrumental

Analyses, University of Patras, Patras, Greece.

Representative procedures for the acylation of erythritol,

glycerol, and pentaerythritol with RCOOH/DCC/DMAP,

(RCO)2O/DMAP, RCOCl/py, and RCOCl/BF3 � Et2Oand spectroscopic data of the products are provided as sup-

porting information. Yields, melting points, and elemental

analyses are presented in Table 1

3 Results and discussion

3.1 The acylation of meso-erythritol

Erythritol is practically insoluble in CH2Cl2 and CHCl3(which is the best solvent for acylations, e.g., with

(RCO)2O/DMAP [25]), and it has a slight solubility in

DMF (�150 mL/g) and in pyridine (40 mL/g [1]). The last

two solvents, although convenient for small scale acylations,

become expensive and difficult to remove when in large

amounts. The coarse crystals of erythritol do not react easily

and finely ground erythritol, too, is completely acylated slowly

(�6–7 days) at room temperature (RT). In all acylations we

carried out, the acylating systems were only in slight excess.

With RCOOH/DCC/DMAP the acylation of erythritol

either in CH2Cl2 or in DMF always produced some N-acy-

lurea which lower the yields, Table 1. The tetrastearate 1,

being sparingly soluble in CH2Cl2, co-precipitates with

DHU, but it is separated from DHU by extraction with

CHCl3. In order to obtain pure products 1 and 3 with this

1358 P. V. Ioannou et al. Eur. J. Lipid Sci. Technol. 2011, 113, 1357–1362


acylating system the removal ofN-acylurea is done by recrys-

tallization from methanol, followed by a recrystallization

from acetone, Table 1. With (RCO)2O/DMAP as acylating

system the yields were�90%, Table 1, but its disadvantage is

that half of the acid is lost. The acylation of an alcohol with

RCOCl/py should be done at low temperatures because of the

possible formation of by-products (e.g., chlorinated ones) by

analogy to the tosylation of an alcohol [26] and acylation by

RCOCl of sn-glycero-3-phosphorylcholine [27]. The acyla-

tion of erythritol by oleoyl chloride was done at RT but with

very slow addition of the oleoyl chloride. In this preparation

we encountered severe emulsification in the washing steps

and the removal of the excess of the formed oleic acid was

not efficient. It was, however, removed during the

column chromatographic isolation of 1 (R ¼ C17H33). The

yields are satisfactory, Table 1, except in the case of

1 (R ¼ C9H19) where portion of lipid was lost in the recrys-

tallization step.

The so-called ‘‘boron trifluoride-alcohol complexes’’ in

excess alcohol have been used for the esterification of carbox-

ylic acids [28, 29]. Because this system is not suitable for the

acylation of erythritol, we turned to the RCOCl/

BF3 � Et2O system which was used by Darin et al. [30] to

acylate ferrocene (a Friedel–Crafts ketone synthesis reac-

tion). As shown in Table 1, with this system the yields are

inferior, e.g., with pentaerythritol with four primary –OH

groups. Moreover, the case of erythritol points toward dimin-

ished ability to acylate the secondary –OH group(s). In this

system the true catalyst is the Hþ because its removal by zinc

dust further diminished the yields.

Table 1. Reaction conditions for the complete acylation of meso-erythritol, glycerol, and pentaerythritol according to the acylated system

and data of the produced esters

Substrate

Acylating

system

R of the

acylating

agent

Reaction

solvent

Reaction

conditions

Yield

(%)

Melting

point

(8C)

Molecular

formula Mr

Elemental analyses

Calcd (Found)

C H

Erythritol A C17H35 CH2Cl2 RT/6 days 82 87–88a) C76H146O8 1187.97 76.84

(76.59)

12.39

(12.59)

C15H31 CH2Cl2 RT/16 days 56j) 82–84b) C68H130O8 1075.72 75.92

(76.28)

12.18

(11.92)

Erythritol B C13H27 DMF/CH2Cl2 1.5/5 Reflux/18 h 81 74–75c) C60H114O8 963.54 74.79

(74.86)

11.93

(11.70)

C11H23 DMF/CH2Cl2 RT/3 days 89 66–68d) C52H98O8 851.33 73.36

(73.31)

11.60

(11.57)

Erythritol C C17H33 CH2Cl2 RT/6 days 82 Liquid C76H138O8 1179.86 77.36

(77.40)

11.79

(11.92)

C11H23 CH2Cl2 RT/6 days 88 67–68d)

C9H19 CH2Cl2 RT/6 days 60 56–58d) C44H82O8 739.10 71.50

(71.40)

11.18

(11.23)

Erythritol D C15H31 CH2Cl2 RT/7 days 74 71–72e)

Glycerol C C17H35 Pyridine RT/9 days 72 70–72f),k)

Pentaerythritol A C17H35 CH2Cl2 RT/6 days 78 76–78g),l)

Pentaerythritol C C17H35 CH2Cl2 RT/7 days 100 75–76h)

Pentaerythritol D C15H31 CH2Cl2 RT/7 days 47 69–71i),m)

Acylating systems: A, RCOOH/DCC/DMAP; B, (RCO)2O/DMAP; C, RCOCl/pyridine; D, RCOCl/BF3 � Et2O. The fatty acid anhydrides

or chlorides were in slight excess.

Recrystallization solvents for the crude product:a) (a) 50 mL MeOH/g, (b) 250 mL Me2CO/gb) 100 mL Me2CO/gc) 60 mL Me2CO/gd) 20 mL Me2CO/ge) Twice recrystallized (100 mL Me2CO/g); still impure by m.p.f) 40 mL Me2CO/g of product pre-purified by column chromatographyg) (a) 60 mL MeOH/g, (b) 200 mL Me2CO/gh) 50 mL Me2CO/g without removing py � HCli) 55 mL Me2CO/gj) Not pulverized erythritolk) m.p. 728C [24]l) m.p. 76–778C [9]m) m.p. 69.5–708C [9]

Eur. J. Lipid Sci. Technol. 2011, 113, 1357–1362 Fully esterified erythritol 1359


Pure products with saturated acyl chains 1 were obtained

by recrystallization from acetone in quantities shown in

Table 1. The purity was checked by TLC (CHCl3/MeOH

20:1, Rf 0.77; Et2O/peth 1:3, Rf 0.70) and1H NMR (Section

3.2). The tetraoleoyl 1 being an oil could only be purified by

column chromatography, where the oleic acid impurity was

totally removed.

3.2 Properties of the esters 1, 2, and 3

All tetraesters 1 with saturated fatty acyl chains examined are

soluble in CHCl3 and, except for 1 (R ¼ C17H35), are also

soluble inCH2Cl2. They are sparingly soluble in Et2O, except

1 (R ¼ C9H19) which is quite soluble. They are insoluble in

acetone at RT but soluble in boiling acetone and they were

recrystallized from this solvent, Table 1. All are insoluble in

DMF, 95% EtOH, and MeOH at RT. In warm MeOH and

95% EtOH 1 (R ¼ C9H19) is soluble. The tetraoleoyl 1 is

insoluble in DMF, MeOH and 95% EtOH.

The melting points of the tetraesters of meso-erythritol 1

all having even number of carbon atoms in their acyl chain are

higher, Fig. 1, than those of the tetraesters of pentaerythritol 3

with both even and odd carbon atoms in their chain [9]. The

triesters of glycerol 2 havemelting points [1, 31] quite close to

those of the corresponding esters 3. Interestingly, the tetraa-

cetate ester of 1 melts at 86–888C [6], quite out of the trend

seen in Table 1, and is about the same as the melting point of

the tetraacetate ester 3 (84–868C) [9]. For the esters 3 the

melting points decreased from the tetraacetate to tetrapen-

tanoate (m.p. �148C) and then increased [9].

The solid state IR spectra of the tetraesters 1

(R ¼ C17H35, C15H31, and C13H27) showed the carbonyl

absorption as a single band at 1730 cm�1 while in 1 with

R ¼ C11H23 and C9H19 this band was split into two, 1738

and 1726 cm�1, with equal intensities, Fig. 2A, due to

RCOOCH2– and to RCOOCH<, respectively. In the IR

spectra of the prepared 2 and 3 the carbonyl absorption

was at 1736 cm�1. The IR spectrum of the oily tetraester

1 showed very weak absorptions for the C––C stretching

(1685 cm�1) and ––CH bending (1407 and 692 cm�1) but

a characteristic ––CH stretching (3004 cm�1) of medium

intensity. These bands were absent in the octabrominated

derivative.

The 1H NMR spectra of the tetraesters 1 with saturated

fatty acyl chains in CDCl3 showed sharp absorptions,

Fig. 2B. The RCOOCH peak is somewhat broad at

5.271 ppm, while the RCOOCH2 protons resonate as a pair

of doublet of doublets at 4.34 ppm (except for R ¼ C9H19

which resonates at 4.30 ppm) and 4.14 ppm. This splitting,

seen in many kinds of lipids is probably due to a non-equal

shielding of the geminal protons caused by the orientation of

the CH2–OCOR bond [32]. The tristearin 2 in CDCl3

Figure 1. Capillarymelting points of tetraesters ofmeso-erythritol 1

(cycle) (this work) compared to the tetraesters of pentaerythritol 3

with an even (solid rectangle) and odd (solid triangle) carbon atoms

in each acyl chain [9] and to triglycerides 2 (solid cycle) [1, 31]. The

melting points of the tetraacetates of 1 and 3 were well out of the

curves: 86–888C [6] and 84–858C [9], respectively. Our m.p. for 2

(R ¼ C17H35) (þ) is quite close to that of the literature (solid cycle).

Figure 2. (A) the IR (KBr) spectrumof the tetraester 1 (R ¼ C11H23)

showing two bands for the carbonyl stretching. (B) Part of the1H NMR (CDCl3) spectrum of 1 (R ¼ C17H35) showing the well

resolved glycerol backbone and the RCH2COO– hydrogens. (C)

The 13C NMR spectrum of 1 (R ¼ C15H31). The four carbonyl car-

bons are not separated because of the meso-erythritol backbone.



showed the RCOOCH proton as an 7-plet at 5.264 while the

RCOOCH2 protons gave the above mentioned pattern cen-

tered at 4.30 and 4.14 ppm. Such a pattern was not observed

in the spectra of 3where the RCOOCH2 protons resonated as

a sharp singlet at 4.106 ppm. The 1H NMR spectrum of the

tetraoleoyl 1 showed a multiplet at 5.34 ppm, due to

–CH2–CH ¼ CH–CH2– protons, well separated from the

multiplet at 5.37 ppm due to the two RCOOCH protons.

As expected, the 1H NMR spectrum of its octabromo deriva-

tive, obtained from bromination of the tetraoleoyl 1, showed

no absorbance at 5.34 ppm, while the new absorbance at

4.22 ppm is assigned to the CH2CHBrCHBrCH2 protons.

The 13C NMR spectrum, obtained for 1 (R ¼ C15H31),

Fig. 2C, showed only one signal for each carbon of the

molecule due to its symmetry. The 13C NMR spectrum of

the tetraoleoyl 1 showed the expected absorptions for the

carbons of the double bond (129.71 and 130.02) and the

methylene carbons attached directly to this double bond

(27.23 and 27.19). The remaining signals in the spectrum

are similar to that of the tetrapalmitate ester 1. Finally, in the13C NMR spectrum of the octabromo derivative of the tet-

raoleoyl 1, the alkene carbon signals at 129.71 and 130.02

completely disappeared and two new absorptions at 59.71

and 59.80 appeared assigned to the CH2CHBrCHBrCH2

carbons.

Attempts at obtaining crystals suitable for X-rays by crys-

tallization from acetone were not successful. Thus, the esters

1 (R ¼ C17H35 and R ¼ C13H27) gave cotton-like and fluffy

precipitates, respectively, while the esters 1 (R ¼ C11H23 and

R ¼ C9H19) gave crystals that were not suitable for X-rays.

The ester 3 (R ¼ C17H35) gave a cotton-like precipitate while

that of 3 (R ¼ C15H31) gave crystals not suitable for X-rays.

Preliminary experiments at epoxidation of tetraoleoyl 1 as

a suspension in absolute ethanol by dropwise addition of a

solution of m-chloroperbenzoic acid in absolute ethanol and

work up gave, by TLC (Et2O/peth 1:3) many spots with Rf

values starting from �0 up to 0.75 (Rf of starting material in

the above system 0.83). Column chromatography of the oily

mixture gave fractions which were analyzed by electrospray

mass spectra. The mass spectra of all of these fractions

showed that they were not pure compounds but mixtures

even in cases where one spot was detectable by TLC.

According to the mass spectrum, the tetraepoxidized tetrao-

leoyl 1 was the main product of the fraction with Rf value of

�0.07 (Et2O/peth 1:3). Therefore, this reaction requires a

more detailed investigation in order to increase the yields by

suppressing the formation of by-products. In sharp contrast

to the epoxidation, the bromination of the unsaturated 1 was

smooth and quantitative.

4 Conclusions

Four acylating systems were tried for the acylation of the

dichloromethane-insoluble meso-erythritol in order to see

their efficacy in terms of reaction time and yields. From them,

clearly inferior is the RCOCl/BF3 � Et2O acylating system

which gave low yields and showed diminished capability to

acylate a secondary hydroxyl group. Ranking the other three

systems, Table 1, for the rate of acylation was not possible

because the progress could not be followed byTLCdue to the

uncertainty of when all secondary hydroxyl groups of eryth-

ritol had reacted but the RCOCl/py acylating system seems

both simpler and efficient. For practical uses unsaturated

tetraesters of erythritol may be more useful than the saturated

ones and if the stereochemistry is not significant tetritol

mixtures (erythritol plus threitols) can be prepared via epox-

idation/hydrolysis of the much cheaper 1,3-butadiene.

Saturated tetraesters, can have applications analogous or

even different to saturated triglycerides based on their

physical, chemical, and biochemical properties.

5 Note added in proof

During the revision of this paper, we came across a paper by

Sari et al. [33] where it is claimed that they prepared the

tetrastearoyl and tetrapalmitoyl esters of erythritol without

stating degrees of purification, yields and elemental analyses

of the products. Moreover, their data (melting points and 1H

NMR spectra) are inconsistent with the claimed compounds.

The IR spectra cannot differentiate between, e.g., esters of

erythritol and ethylene glycol.Data which differentiate between

these esters are shown in this paper (Table 1 and Fig. 2).

The authors have declared no conflict of interest.

References

[1] Windholz, M. (Ed.) The Merck Index, 9th Edn., Merck andCo., Rahway, New Jersey (USA) 1976.

[2] Gurr, M. I., James, A. T., Lipid Biochemistry: An Introduction,Chapman and Hall, London (England) 1971.

[3] Li, Y., Fu, L., Lai, S., Cai, X., Yang, L., Synthesis andcharacterization of cast resin based on different saturationepoxidized soybean oil. Eur. J. Lipid Sci. Technol. 2010, 112,511–516.

[4] Munro, I. C., Berndt, W. O., Borzelleca, J. F., Flamm, G.,et al., Erythritol: An interpretive summary of biochemical,metabolic, toxicological and clinical data. Food Chem.Toxicol. 1998, 36, 1139–1174, Erratum in Food Chem.Toxicol. 1999, 37, I–II.

[5] Ohle, H., Melkonian, G. A., Die benzoylierung des erythritsund darstellung von derivaten des O-benzoyl-glykolaldehyds.Chem. Ber. 1941, 74, 291–294.

[6] Wolform, M. L., Bower, R. S., Maher, G. G., A simple ace-tolysis of nitrate esters. J. Am. Chem. Soc. 1951, 73, 874–875.

[7] Schalit, J., The esterification of inactive, non-splitting eryth-ritol with palmitic and stearic acids. Wiss. Mitt. Osterreich.Heilmittelstelle. 1929 and 1930, 42–44 and 5–10.Chem. Abstr.1932, 26, 4303–4304.

[8] Neissner, R., Herstellung, Analyse und DC-Trennung vonFettsaure-Erythritpartialestern. Fette Seifen Anstrichmittel.1980, 82, 10–16.

Eur. J. Lipid Sci. Technol. 2011, 113, 1357–1362 Fully esterified erythritol 1361


[9] Breusch, F. L., Oguzer, M., Darstellung der di-, tri- undtetra-homologen Reihen der Methan-methylol-fettsaur-eester. Chem. Ber. 1955, 88, 1511–1519.

[10] Haslam, E., Recent developments in methods for the ester-ification and protection of the carboxylic group. Tetrahedron1980, 36, 2409–2433.

[11] March, J., Advanced Organic Chemistry, 3rd Edn., Wiley-Interscience, New York (USA) 1985, p. 337.

[12] Hofle, G., Steglich, W., Vorbruggen, H., 4-Dialkylaminopyridines as highly active acylation catalysts.Angew. Chem. Int. Ed. Eng. 1978, 17, 569–583.

[13] Scriven, E. F. V., 4-Dialkylaminopyridines: Super acylationand alkylation catalysts. Chem. Soc. Rev. 1983, 12, 129–161.

[14] Khorana, H. G., Carbodiimides. Part III. (A) A new methodfor the preparation of mixed esters of phosphoric acid. (B)Some observations on the base catalysed addition of alcoholsto carbodiimides. Can. J. Chem. 1954, 32, 227–234.

[15] Smith, M., Moffatt, J. G., Khorana, H. G., Carbodiimides.VIII. Observations on the reaction of carbodiimides withacids and some new applications in the synthesis of phos-phoric acid esters. J. Am. Chem. Soc. 1958, 80, 6204–6212.

[16] Amat, F., Martinez Utrilla, R., Olano, A., Reaction of N,N0-dicyclohexylcarbodiimide with fatty acids in the presence ofalcohols. Anal. Quim. 1969, 65, 829–832.

[17] Neises, B., Steglich, W., Simple method for the esterificationof carboxylic acids. Angew. Chem. Int. Ed. Eng. 1978, 17,522–523.

[18] Moore, J. S., Stupp, S. I., Room temperature polyesterifica-tion. Macromolecules 1990, 23, 65–70.

[19] Mitsunobu, O., The use of diethyl azodicarboxylate andtriphenylphosphine in the synthesis and transformation ofnatural products. Synthesis 1981, 1–28.

[20] Hughes, D. L., Reamer, R. A., Bergan, J. J., Grabowski, E. J.J., A mechanistic study of the Mitsunobu esterification reac-tion. J. Am. Chem. Soc. 1988, 110, 6487–6491.

[21] Mitsunobu, O., Kimura, J., Iiizumi, K., Yanagida, N.,Stereoselective and stereospecific reactions. III.Benzoylation, cyclization, and epimerization of diols. Bull.Chem. Soc. Japan. 1976, 49, 510–513.

[22] Lapidot, Y., Barzilay, I., Hajdu, J., The synthesis of diacyl-DL-(and -L-)a-glycerol phosphate. Chem. Phys. Lipids 1969,3, 125–134.

[23] Gupta, C. M., Radhakrishnan, R., Khorana, H. G.,Glycerophospholipid synthesis: Improved general methodand new analogs containing photoactivable groups. Proc.Natl. Acad. Sci. USA 1977, 74, 4315–4319.

[24] Dasaradhi, L., O’Hagan, D., Petty, M. C., Pearson, C.,Synthesis and characterization of selectively fluorinated stea-ric acids and their tristearins: The effect of introducing oneand two fluorine atoms into a hydrocarbon chain. J. Chem.Soc. Perkin Trans. 1995, 2, 221–225.

[25] Mangroo, D., Gerber, G. E., Phospholipid synthesis: Effectsof solvents and catalysts on acylation. Chem. Phys. Lipids1988, 48, 99–108.

[26] Timpson, R. S., On esters of p-toluenesulfonic acid. J. Org.Chem. 1944, 9, 235–241.

[27] Aneja, R., Chadha, J. S., Acyl-chloro-deoxyglycerophos-phorylcholines: Structure of the so-called cyclic lysolecithins.Biochim. Biophys. Acta. 1971, 239, 84–91.

[28] Marshall, J. L., Erickson, K. C., Folsom, T. K., The ester-ification of carboxylic acids using a boron trifluoride-etherate-alcohol reagent. Tetrahedron Lett. 1970, 4011–4012.

[29] Kadaba, P. K., Boron trifluoride etherate-alcohol, a versatilereagent for the esterification reaction. Synth. Commun. 1974,4, 167–181.

[30] Darin, V. A., Neto, A. F., Miller, J., de Freitas Afonso,M. M., et al., Boron trifluoride etherate as a catalyst inacylation of ferrocene. J. Prakt. Chem. 1999, 341, 588–591.

[31] West, R. C. (Ed.) CRC Handbook of Chemistry and Physics,65th Edn., CRC Press, Boca Raton, Florida (USA) 1985.

[32] Amato,M. E., Irgolic, K. J., Junk, T., Pappalardo,G.C., Perly,B., 1H and 13C NMR spectra of rac-2,3-bis(palmitoyloxy)-propyl(2-trimethylarsonioethyl)phosphonate, an arsenic-con-taining phosphonolipid.Magn. Res. Chem. 1990, 28, 856–861.

[33] Sari, A., Eroglu, R., Bicer, A., Karaipekli, A., Synthesis andthermal energy storage properties of erythritol tetrastearateand erythritol tetrapalmitate. Chem. Eng. Technol. 2010, 34,87–92, DOI: 10.1002/ceat.20100036.



preparation and properties of fully esterified erythritol

Documents