Chemistry of Fatty Acids

Chemistry of Fatty Acids
Charlie Scrimgeour1 , Yue Gao2 , Won Young Oh2 , and Fereidoon Shahidi2
1
The James Hutton Institute, Dundee, Scotland
2
Memorial University of Newfoundland, St. John’s, Newfoundland, Canada
1. INTRODUCTION
Fatty acids, esterified to glycerol backbone, are the main constituents of oils and fats. The
industrial exploitation of oils and fats, both for food and oleochemical products, is based
on chemical modification of both the carboxyl and unsaturated groups present in fatty acids.
Although the most reactive sites in fatty acids are the carboxyl group and double bonds, methy-
lene groups adjacent to them are activated, increasing their reactivity. Only rarely do saturated
chains show reactivity. Carboxyl groups and unsaturated centers usually react independently,
but when in close proximity, both may react through neighboring group participation. In enzy-
matic reactions, the reactivity of the carboxyl group can be influenced by the presence of a
nearby double bond.
The industrial chemistry of oils and fats is a mature technology, with decades of experience
and refinement behind current practices, but by no means it is static. Environmental pressures
demand cleaner processes, and there is a market for new products. Current developments are
in three areas of metabolic and genetic modification technology that produces oil corps more
desirable for industrial use; green chemistry, using cleaner processes, less energy, and renew-
able resources; enzyme-catalyzed reactions, using both environmentally friendly processes
and producing tailor-made products, and novel chemistry to functionalize the carbon chain,
leading to new compounds. Changing perceptions of what is nutritionally desirable in fat-based
products also drives changing technology; interesterification as well as fractionation by frac-
tional crystallization are more widely used and have largely replaced partial hydrogenation in
the formulation of some modified fats.
The content of this article is somewhat selective, focusing on aspects of fatty acid and lipid
chemistry relevant to the analysis and industrial exploitation of oils and fats. The emphasis is
Bailey’s Industrial Oil and Fat Products, Seventh Edition, edited by Fereidoon Shahidi.
Copyright © 2020 John Wiley & Sons, Ltd.
DOI: 10.1002/047167849X.bio005.pub2
1
2 CHEMISTRY OF FATTY ACIDS
on fatty acids and acylglycerols found in commodity oils and the reactions used in the food
and oleochemical industries. The practical application of this chemistry is detailed in other
articles. Current areas of research, either to improve existing processes or to develop new
ones, are also covered, a common theme being the use of chemical and enzyme catalysts.
Compounds of second-row transition metals rhodium and ruthenium and the oxides of rhenium
and tungsten have attracted particular interest as catalysts for diverse reactions at double bonds.
Recent interest in developing novel compounds by functionalizing the fatty acid chain is also
mentioned. To date, few of these developments have found industrial use, but they suggest
where future developments are likely. A number of reviews and books cover and expand on
topics discussed here [1–12].
2. COMPOSITION AND STRUCTURE
2.1. Fatty Acids

Fatty acids are almost entirely straight-chain aliphatic carboxylic acids. The broadest definition
includes all chain lengths, but most natural fatty acids are C4 to C22 , with C18 being most
common. Naturally occurring fatty acids share a common biosynthesis. The chain is built from
two carbon units, and cis double bonds are inserted by desaturase enzymes at specific positions
relative to the carboxyl group. This results in even-chain-length fatty acids with a characteristic
pattern of methylene interrupted cis double bonds. A large number of fatty acids varying in
chain length and unsaturation result from this pathway.
Systematic names for fatty acids are too cumbersome for general use, and shorter alterna-
tives are widely used. Two numbers separated by a colon give, respectively, the chain length
and number of double bonds: octadecenoic acid with 18 carbons and 1 double bond is there-
fore 18:1. The position of double bonds is indicated in a number of ways: explicitly, defin-
ing the position and configuration; or locating double bonds relative to the methyl or car-
boxyl ends of the chain. Double-bond position relative to the methyl end is shown as n − x
or 𝜔x, where x is the number of carbons from the methyl end. The n-system is now pre-
ferred, but both are widely used. The position of the first double bond from the carboxyl
end is designated Δx. Common names (Table 1) may be historical, often conveying no struc-
tural information, or abbreviations of systematic names. Alternative representations of linoleic
acid [1] are 9Z,12Z-octadecadienoic acid; 18:2 9c12c; 18:2 n-6; 18:2 𝜔6; 18:2 Δ9, 12; or
CH3 (CH2 )4 CH CHCH2 CH CH(CH2 )7 COOH.
18
COOH
12 9 1
1
The terms cis and trans, abbreviated c and t, are used widely for double-bond geometry;
as with only two substituents, there is no ambiguity that requires the systematic Z/E conven-
tion. An expansive discussion of fatty acid and lipid nomenclature and structure appears in
Akoh [1].
Over 1000 fatty acids are known, but 20 or less are encountered in significant amounts in
the oils and fats of commercial importance (Tables 1 and 2). The most common acids are C16
and C18 . Below this range, they are characterized as short or medium chain and above it as
long-chain acids.
COMPOSITION AND STRUCTURE 3
TABLE 1. Fatty acids in commodity oils and fats (nomenclature and structure).
Fatty acid Common name Formula Chain length
4:0 Butyric CH3 (CH2 )2 CO2 H Short

6:0 Caproic CH3 (CH2 )4 CO2 H Short
8:0 Caprylic CH3 (CH2 )6 CO2 H Short/medium
10:0 Capric CH3 (CH2 )8 CO2 H Medium
12:0 Lauric CH3 (CH2 )10 CO2 H Medium
14:0 Myristic CH3 (CH2 )12 CO2 H Medium
16:0 Palmitic CH3 (CH2 )14 CO2 H
18:0 Stearic CH3 (CH2 )16 CO2 H
18:1 9c Oleic CH3 (CH2 )7 CH CH(CH2 )7 CO2 H
18:2 9c12c Linoleic CH3 (CH2 )4 (CH CHCH2 )2 (CH2 )6 CO2 H
18:3 9c12c15c α-Linolenic CH3 CH2 (CH CHCH2 )3 (CH2 )6 CO2 H
22:1 13c Erucic CH3 (CH2 )7 CH CH(CH2 )11 CO2 H Long
20:5 5c8c11c14c17c EPA1 CH3 CH2 (CH CHCH2 )5 (CH2 )2 CO2 H Long
22:5 DPA1 Long
22:6 4c7c10c13c16c19c DHA1 CH3 CH2 (CH CHCH2 )6 CH2 CO2 H Long
Abbreviations of the systematic names eicosapentaenoic acid, docosapentaenoic acid, and docosahexaenoic acid.
TABLE 2. Occurrence.
Fatty acid Significant sources
4:0 Butter, dairy fats

6:0 (Coconut, palm kernel)
12:0 Coconut, palm kernel
14:0 Coconut, palm kernel
16:0 Cottonseed, palm
18:0 Cocoa butter, tallow
18:1 9c Cottonseed, olive, palm, rape
18:2 9c12c Corn, sesame, soybean, sunflower
18:3 9c12c15c Linseed
20:1 13c High erucic rape
20:5 5c8c11c14c17c Fish and animal fats
22:6 4c7c10c13c16c19c Fish and animal fats
Fatty acids with trans or non-methylene-interrupted unsaturation occur naturally or are

formed during processing; for example, vaccenic acid (18:1 11t) and the conjugated linoleic
acid (CLA) rumenic acid (18:2 9t11c) are found in dairy fats. Hydroxy, epoxy, cyclopropane,
cyclopropene acetylenic, and methyl branched fatty acids are known, but only ricinoleic acid
(12(R)-hydroxy-9Z-octadecenoic acid) [2] from castor oil is used for oleochemical production.
Oils containing vernolic acid (12(S),13(R)-epoxy-9Z-octadecenoic acid) [3] have the potential
for industrial use.
OH
COOH
2
H O H
COOH
3
TABLE 3. Fatty acid composition of different types of common commodity oil and fats (% w/w).
Type of oil/fat Percentage of total fatty acid
C4:0 C6:0 C8:0 C10:0 C12:0 C14:0 C16:0 C18:0 C20:0 SFA MUFAs PUFAs
Almond 0.09 0.07 6.8 2.3 0.09 9.3 67.9 22.8

Butter 4 2 1 3 3 11 27 12 66 31 3
Caster 1 1 2 91.35 6.15
Coconut 0.04 7.0 8.0 48.0 16.0 9.2 2.0 0.25 92.1 6.2 1.6
Corn 4.0 7.0 0.6 10 3.5 25.1 26.8 48
Cottonseed 0.4 20 2.0 22.4 35.4 42
Grape 0.01 0.01 0.05 6.6 3.5 0.16 10.4 14.8 74.9
Hemp 0.07 6.4 2.6 9.2 28.1 62.8
Linseed 5.5 3.5 0.65 9.65 22.1 68
Milk thistle 0.01 0.09 7.9 2.3 0.43 19.4 68.2 18.0
Olive 16.5 2.0 0.22 14.35 78.4 7.0
Palm kernel 4.0 5.0 41 ± 5.0 16.0 8 2.0 76 22.5 1.25
Peanut 0.04 7.5 2.1 1.0 10.7 71.1 18.2
Pumpkin seed 0.17 13.1 5.7 0.47 19.6 26.1 54.3
Rice barn 0.39 20.0 2.1 22.5 44.0 33.6
Soybean 0.5 9 4.0 13.5 28.5 57.5
Sunflower 3.7 2.0 2.3 8.8 31.5 59.5
Safflower 0.5 4.0 2.5 0.2 9.4 28.3 62.4
Sesame 9.7 6.5 0.63 16.9 42 41.2
Rapeseed 0.01 4.6 1.7 6.3 72.8 20.9
Canola type 1 5.2 4.4 9.6 59.5 30.7
Canola type 2 10.5 6.9 17.4 23.2 59.2
Wheat germ 0.07 17.4 0.7 18.2 20.9 61.0
Salmon 5.8 13.6 1.7 0.1 21.2 50.6 25.5
Typical midrange values are shown; the balance is minor components.

Source: Data from [9, 133–136].
Most commodity oils contain fatty acids with chain lengths between C16 and C22 , with
C18 fatty acids dominating in most plant oils (Table 3). Palm kernel and coconut, sources of
medium-chain fatty acids, are referred to as lauric oils. Animal fats have a wider range of
chain length, and high erucic varieties of rape are rich in this C22 monoene acid. Potential
new oil crops with unusual unsaturation or additional functionality are under development.
Novel technologies in industrial processing have found more use for common oil crops and
their by-products. Compilations of the fatty acid composition of oils and fats [6, 9, 13, 14] and
less-common, novelty oil sources [15] are available.
The basic structure, a hydrophobic hydrocarbon chain with a hydrophilic polar group
at one end, endows fatty acids and their derivatives with distinctive properties, reflected in
both their food and industrial use. Saturated fatty acids have a straight hydrocarbon chain.
A trans-double bond is accommodated with little change in shape, but a cis bond introduces
a pronounced bend in the chain (Figure 1).
In the solid phase, fatty acids and related compounds pack with the hydrocarbon chains
aligned and, usually, the polar groups together. The details of the packing, such as the unit
cell angles and head-to-tail or head-to-head arrangement depend on the fatty acid structure
(Figure 2).
The melting point increases with chain length and decreases with increased unsaturation
(Table 4). Among saturated acids, odd chain acids are lower melting than adjacent even chain
acids. The presence of cis-double bonds markedly lowers the melting point, the bent chains
(a)
(b)
(c)
Figure 1. “Ball and stick” models of (a) stearic acid, 18:0; (b) elaidic acid, 18:1 9t; and (c) oleic acid 18:1
9c. All three lie flat in the plane of the paper. The cis double bond causes a distinct kink in the alkyl chain
of oleic acid.
(a) (b) (c) (d)
Figure 2. Simplified diagram shows packing patterns of fatty acids in the solid phase. (a,b) Hydrocarbon
tails (straight lines) aligned at different angles to the line of the polar head groups (circles); (c) head-to-tail
packing; and (d) head-to-head packing.
packing less well. Trans-acids have melting points much closer to those of the corresponding
saturates. Polymorphism results in two or more solid phases with different melting points.
Methyl esters are lower melting than fatty acids but follow similar trends.
Fatty acid salts and many polar derivatives of fatty acids are amphiphilic, possessing both
hydrophobic and hydrophilic areas within the one molecule. These are surface-active com-
pounds that form monolayers at water/air and water/surface interfaces and micelles in solution.
TABLE 4. Averaged melting points of some fatty acids and their methyl esters
to illustrate the effect of chain length, degree of unsaturation and configuration.
Fatty acid Averaged melting point Methyl esters
8:0 16.3 −38.6

9:0 12.3 −35
10:0 31.5 −15.7
11:0 28.6 5.1
11:1 24.5 −27.5
12:0 43.8 6.2
14:0 55.1 18.7
14:1 Δ9c −4.3
15:0 52.7 18.8
16:0 63.0 30.1
16:1 Δ9c −0.03
16:1 Δ9t 32.5
17:0 61.7 29.8
18:0 69.7 38.9
18:1 Δ6c 30.0
18:1 Δ6t 54.1
18:1 Δ9c 13.2 −19.9
18:1 Δ9t 45.5 13.5
18:1 Δ11c 14.2
18:1 Δ11t 44.0
18:2 Δ9c , Δ12c −5 −35
18:3 Δ9c , Δ12c , Δ15c −11 −45.5
19:0 69.0 39.7
20:0 76.0 47.4
21:0 74.3 48.1
22:0 80.6 53.2
23:0 79.3 54.5
24:0 86.3 58.7
Source: Adapted from [137] and data was from [138–147].
Their surface-active properties are highly dependent on the nature of the polar head group and,
to a lesser extent, on the length of the alkyl chain. Most oleochemical processes are modifica-
tions of the carboxyl group to produce specific surfactants, lubricants, solvents, biodiesel, and
bioplastics [16].
2.2. Acylglycerols
Fatty acids in oils and fats are found esterified to glycerol. Glycerol (1,2,3-trihydroxypropane)
is a prochiral molecule. It has a plane of symmetry, but if the primary hydroxyls are esterified
to different groups, the resulting molecule is chiral and exists as two enantiomers. The
stereospecific numbering system is used to distinguish between enantiomers. The Fischer
projection of glycerol is drawn with the backbone bonds going into the paper and the
hydroxyl on the middle carbon to the left. The carbons are then numbered 1–3 from the top
(Figure 3). The prefix sn- (for stereospecific numbering) denotes a particular enantiomer,
rac- an equal mixture of enantiomers, and x- an unknown stereochemistry. In an asymmetric
environment such as an enzyme binding site, the sn-1 and sn-3 groups are not interchangeable
and reaction will only occur at one position. Simplified structures are often used; e.g.
CH2OH sn-1 (α) CH2OOCR P

HO H sn-2 (β) R'COO H e.g. L
CH2OH sn-3 (α) or (α′) CH2OOCR′′ O
Stereospecific numbering Triacylglycerol

of glycerol backbone
CH2OOCR CH2OH
HO H RCOO H
CH2OH CH2OH
1-Monoacyl-sn-glycerol 2-Monoacyl-sn-glycerol
(1-MAG) (2-MAG)
CH2OOCR CH2OOCR
R′COO H HO H
CH2OH CH2OOCR′
1,2-Diacyl-sn-glycerol 1,3-Diacyl-sn-glycerol
(1,2-DAG) (1,3-DAG)
CH2OOCH
R′COO H O
CH2O P OX
O–
Phosphatidylcholine X = CH2CH2N+(CH3)3
Phosphatidylethanolamine X = CH2CH2N+H3
Figure 3. Structure and stereospecific numbering of acylglycerols.
TABLE 5. Molecular species of triacylglycerols containing only palmitic and oleic acid.
PPP POP PPO OPP POO OOP OPO OOO
Enantiomers ∗ ∗ ∗∗ ∗∗
Carbon number 48 50 50 50 52 52 52 54
Double bonds 0 1 1 1 2 2 2 3
1-palmitoyl-2-linoleoyl-3-oleoyl-sn-glycerol is abbreviated to PLO or drawn as shown in

Figure 3.
Storage fats (seed oils and animal adipose tissue) consist mainly (∼98%) of triacylglycerols,
with the fatty acids distributed among different molecular species. With only two fatty acids,
a total of eight triacylglycerol isomers are possible, including enantiomers (Table 5). A full
analysis of triacylglycerol molecular species is a major undertaking, and for some oils, there
are still technical difficulties to be resolved. More commonly, triacylglycerols are distinguished
by carbon number (the sum of the fatty acid chain lengths) or degree of unsaturation, using gas
chromatography (GC) or high-performance liquid chromatography (HPLC) for analysis. The
number of isomers increases as the cube of the number of fatty acids; hence, even in oils with
a simple fatty acid composition, many molecular species of triacylglycerol may be present.
TABLE 6. Contrasting triacylglycerol composition of some commodity oils [Molecular Species

(wt %)].
Cocoa butter Coconut Lard Olive Soybean
POP (18–23) 12, 12, 8 (12) PPSt (2) OOL (11) LnLL (7)
POSt (36–41) 12, 12, 10 (6) StPSt (2) OOO (43) LnLO (5)
StOSt (23–31) 12, 12, 12 (11) PPO (8) POP (3) LLL (15)
12, 12, 14 (11) StOP (13) POL (4) LLO (16)
Unsymmetrical e.g. SSO <1% 14, 12, 8 (9) POO (5) POO (22) LLS (13)
StOO (6) StOO (5) LOO (8)
OPO (18) LOS (12)
StPL (2) OOS (5)
OOO (12)
OPL (7)
L, linoleic; Ln, linolenic; O, oleic; P, palmitic; S, saturate; St, stearic; 8, 8:0; 10, 10:0; 12, 12:0 (lauric); 14, 14:0.
Analysis by methods that do not distinguish all isomers; only major components are listed.
Data from [6].
Different methods of analysis will give different and often incomplete information about
such a mixture. GC analysis will separate molecular species by carbon number (sum of fatty
acid chain lengths). Silver-ion HPLC will separate by number of double bonds. Stereospecific
analysis measures the proportions of fatty acids at the sn-1, sn-2, and sn-3 positions, but it
does not detect individual molecular species. GC and HPLC analyses are often used together
to produce a more in-depth detail [17].
Most natural triacylglycerols do not have a random distribution of fatty acids on the glyc-
erol backbone. In plant oils, unsaturated acids predominate at the sn-2 position, with more
saturated acids at sn-1 and sn-3. The distribution of fatty acids at the sn-1 and sn-3 positions is
often similar, although not identical. However, a random distribution between these two posi-
tions is often assumed as full stereospecific analysis is a time-consuming specialist procedure.
In animal fats, the type of fatty acid predominating at the sn-2 position is more variable; for
example, palmitate may be selectively incorporated as well as unsaturated acids (Table 6).
Only oils that are rich in one fatty acid contain much monoacid triacylglycerol, for example
olive (Table 6), sunflower, and linseed oils containing OOO, LLL, and LnLnLn, respectively.
Compilations of the triacylglycerol composition of commodity and other oils are available
[8, 9].
The melting behavior of triacylglycerols generally reflects that expected from the fatty
acid composition; triacylglycerols rich in long-chain and saturated acids are high melting, and
those rich in polyunsaturated acids are lower melting. However, the situation is complicated
by the possibility that the fatty acids can be distributed in different molecular species with
different melting points. Oils with similar fatty acid composition may have different solid fat
content, polymorphic forms, and melting behavior as a result of a different triacylglycerol
composition.
Mono- and diacylglycerols (Figure 3) are not significant components of good quality oils,
but elevated levels may be found in badly stored seeds, resulting from the activity of lipolytic
enzymes. These compounds are produced industrially by partial hydrolysis or glycerolysis of
triacylglycerols for use as food-grade emulsifiers. Mono- and diacylglycerols readily isomerize
under acid or base catalysis and are normally produced as an equilibrium mixture in which
1(3)-monoacylglycerols or 1,3-diacylglycerols predominate.
HYDROLYSIS, ESTERIFICATION, AND ESTER EXCHANGE 9
Phospholipids (Figure 3) are constituents of membranes and are only minor components of
oils and fats, sometimes responsible for cloudiness. They are usually removed during degum-
ming, the residue from soybean oil processing being a source of phospholipids used as food
emulsifiers. The term “lecithin” is used very loosely for such material, and it may variously
mean phosphatidylcholine, mixed glycerophospholipids, or crude phospholipid extracts from
various sources. Where possible, more specific nomenclature or the source and purity should
be used [18].
2.3. Bulk Properties

Saponification value (SV) and iodine value (IV). Oils and fats are now characterized mainly
by their fatty acid composition determined by GC, replacing the titrimetric and gravimetric
assays used previously. However, the SV or saponification equivalent (SE) and IV are still
used in specifications and to monitor processes. SE, expressed as grams of fat saponified by
one mole of potassium hydroxide, is an indication of the average molecular weight of all the
fatty acids present and hence chain length. Whereas the IV, expressed as the weight percent of
iodine consumed by the fat in a reaction with iodine monochloride, is an index of unsaturation
(Table 7). Standard analytical methods are available [19], but these parameters are now often
calculated from the fatty acid composition, assuming that the sample is all triacylglycerol [19].
Indirect measurement of IV [20, 21] and SV [21] (as well as peroxide and trans-content) using
FT-NIR spectroscopy has been developed for real-time process monitoring.
Unsaponifiable matter. Oils and fats contain variable amounts of sterols, hydrocarbons,
tocopherols, carotenoids, and other compounds, collectively referred to as unsaponifiable
matter because they do not produce soaps upon hydrolysis (Table 7). The sterol and toco-
pherol composition of commodity oils is discussed in another article. Some of these minor
components are removed during refining, and the resulting concentrates may be useful
by-products, for example tocopherol antioxidants. Common refining processes such as short
path distillation remove unwanted fatty acids and environmental contaminants, but it also
strips the oil of its tocopherol antioxidants, which may become a nutritional and a shelf-life
concern [22].
Characteristic fingerprints of minor components, particularly phytosterols and tocopherols,
are also used to authenticate oils and detect adulteration [23].
3. HYDROLYSIS, ESTERIFICATION, AND ESTER EXCHANGE
Reactions converting acids to esters or vice versa and the exchange of ester groups are among
the most widely used in fatty acid and lipid chemistry (Figure 4). They find applications from
microscale preparation of methyl esters for GC analysis to the industrial production of oleo-
chemicals and biodiesel. The exchange of groups attached to the fatty acid carboxyl is usually
an equilibrium process driven to one product by an excess of one reactant or the removal of
one product, and it is usually carried out with the aid of a catalyst. The catalyst may be an
acid, a base, or a lipolytic enzyme. These reactions produce the fatty acids and methyl esters
that are the starting point for most oleochemical production. As the primary feedstocks are oils
and fats, glycerol is produced as a valuable by-product. Reaction routes and conditions with
efficient glycerol recovery are required to maximize the economics of large-scale production.
TABLE 7. Saponification equivalent (SE), saponification value (SV), iodine value (IV), and
unsaponifiable matter of some commodity oils.
SEa SV IV Unsaponifiable matter

(g oil mol KOH−1 ) (mg KOH g oil−1 ) (100 × g iodine g oil−1 ) (wt%)
Butter 242–267 210–232 26–40 <0.5

Castor 300–319 176–187 81–91
Coconut 212–226 248–265 6–11 <1.5
Corn 288–300 187–195 107–128 1–3
Cottonseed 283–297 189–198 100–115 <2
Fishb 292–312 180–192 142–176 <2
Groundnut (peanut) 286–300 187–196 86–107 <1
Lard 276–292 192–203 45–70 <0.2
Linseed 286–298 188–196 170–203 <2
Olive 286–305 184–196 75–94 <1.5
Palm 268–295 190–209 50–55 <1.3
Palm kernel 221–244 230–254 14–21 <1
Rapec 291–308 182–193 110–126 <0.2
Sesame 288–300 187–195 104–120 <2
Soybean 288–297 189–195 124–139 <1.5
Sunflower 289–298 188–194 118–145 <2
Tallow 281–295 190–200 33–47 <0.5
a SE = 56108 SV−1 .
b Cod liver oil.
c Low erucic rape (Canola).
Data from [13].
RCOOR′ + H2O RCOOH + R′OH (1)

RCOOH + R′OH RCOOR′ + H2O (2)
RCOOR′ + R′′COOH R′′COOR + RCOOH (3)

RCOOR′ + R′′OH RCOOR′′ + R′OH (4)
TAG + glycerol MAG + DAG (5)

Figure 4. Exchange reactions at the carboxyl group (1) hydrolysis, (2) esterification, (3) acidolysis, (4)
alcoholysis, and (5) glycerolysis. The starting ester RCOOR′ will often be a triacylglycerol. MAG, mono-
acylglycerol; DAG, diacylglycerol; TAG, triacylglycerol.
A good example is the intensification method based on a dividing wall column (DWC) used
in the production of biodiesel [24].
There is increasing interest in the use of lipase enzymes for large-scale reactions. Enzyme
reactions require milder conditions, less solvent, and give cleaner products – attributes of
“green chemistry.” Enzymes can exert regio- or stereospecific control overreactions and may
also offer a degree of selectivity for particular fatty acids, not observed with acid or base
catalysts. Although the reactions of the carboxyl group are normally independent of those
of the double bonds in the fatty acid molecule, the presence of a double bond at the Δ4,
Δ5, or Δ6 position often results in slower reaction when a reaction is catalyzed by a lipase.
Lipase-catalyzed reactions are considered in detail below, following a brief description of the
reactions involved.
3.1. Hydrolysis
The reaction can be catalyzed by acid, base, or lipase, but it also occurs as an uncatalyzed reac-
tion between fats and water dissolved in the fat phase at suitable temperatures and pressures.
Base-catalyzed hydrolysis. Historically, soaps were produced by alkaline hydrolysis of oils
and fats, and this process is still referred to as saponification. Soaps are now produced by
neutralization of fatty acids produced by fat splitting (see below), but alkaline hydrolysis may
still be preferred for heat-sensitive fatty acids.
On a laboratory scale, alkaline hydrolysis is carried out with only a slight excess of alkali,
typically 1M potassium hydroxide in 95% ethanol, refluxing for one hour, and the fatty acids
recovered after acidification of the reaction mixture. This is a sufficiently mild procedure that
most fatty acids, including polyunsaturates, epoxides, and cyclopropenes, are unaltered [25].
Fat splitting. The industrial production of fatty acids uses the direct reaction between water
and fats, which proceeds rapidly at ∼250 ∘ C and 2–6 MPa (20–60 bar). Under these conditions,
water is moderately soluble in the oil phase, and stepwise hydrolysis of the triacylglycerols
proceeds without the aid of a catalyst. The reaction is carried out with a countercurrent of water
that removes the glycerol formed, resulting in ∼99% conversion to fatty acids. Glycerol is
recovered from the aqueous phase. Sonntag has reviewed industrial fat splitting in detail [26].
3.2. Esterification
Fatty acids are converted to esters by reaction with an excess of alcohol using an acid catalyst
or a lipase. For the preparation of methyl esters for GC analysis, boron trifluoride, sulfuric acid,
or anhydrous hydrogen chloride in methanol are commonly used [25]. Reaction is complete in
30 minutes at reflux. Propyl and butyl esters are prepared in a similar way with the correspond-
ing alcohols. It is not always possible to use an excess of alcohol, for example, in the synthesis
of triacylglycerols using a protected glycerol. A more reactive fatty acid derivative such as
the acid chloride or anhydride is used, or the fatty acid is reacted directly with the alcohol,
using dicyclohexylcarbodiimide (DCC) plus 4-dimethylaminopyridine (DMAP) as a coupling
agent, for example, in the synthesis of acylglycerols [27]. Some groups in more unusual fatty
acids are acid sensitive, for example epoxides, cyclopropanes, cyclopropenes, and hydroxy
compounds, and methods avoiding acids catalysts are needed. Reaction with diazomethane or
the less hazardous trimethylsilyl-diazomethane are possibilities [25].
3.3. Ester Exchange Reactions

The fatty acid or alcohol groups present in an ester can be exchanged in a number of ways:
by reaction with an excess of other fatty acids (acidolysis), alcohols (alcoholysis), or other
esters (interesterificatio OPL (7)n). Generally, the starting point will be a triacylglycerol, and
these reactions provide routes by which the composition and properties of oils and fats can be
modified.
Acidolysis. This reaction can be acid or enzyme catalyzed and may be used to modify tri-
acylglycerol composition. Acidolysis of an oil containing only C16 and C18 fatty acids with
fatty acids rich in lauric acid (e.g. from palm kernel oil) results in a triacylglycerol enriched in
medium-chain fatty acids.
Alcoholysis. Methanolysis of triacylglycerols is used to prepare methyl esters for fatty
acid analysis, a process frequently referred to as transesterification. This can be acid- or
base-catalyzed, the method being chosen to avoid modifying acid- or base-sensitive fatty
acids and to minimize reaction times. Sterol esters of fatty acids react more slowly than
triacylglycerols, and samples containing them require more vigorous reaction conditions.
The preparation of methyl esters from oils and fats for GC and GC-MS analysis has been
extensively reviewed [25, 28, 29].
Biodiesel is produced on the industrial scale by methanolysis of vegetable oils (usually rape
or soybean) or waste fat, particularly using frying oils. Methanolysis proceeds with modest
amounts of base catalyst, provided the levels of free fatty acid and water in the oil are low
[30, 31]. The fatty acid content may be reduced by physical or chemical treatment before
methanolysis but for waste fats, alternative processes that do not use base catalysis may be
preferred. Lipase-catalyzed methanolysis is less sensitive to fatty acid and water in the oil and
has been tested in batch [32] and fixed-bed reactor [33] conversion of waste oil and grease to
biodiesel.
Glycerolysis, the treatment of triacylglycerols with glycerol and a basic catalyst (sodium
hydroxide or sodium methoxide), is used to produce mono- and diacylglycerols on an industrial
scale. Molecular distillation is used to produce monoacylglycerol (MAG), which is 90–95%
pure and is widely used as an emulsifying agent in foods and other applications.
Interesterification. Interesterification is the intra- and intermolecular exchange of fatty acids
on the glycerol backbone of triacylglycerols, although the term is also used more loosely to
include acidolysis and other ester exchange reactions. It is applied to either an individual oil
or a blend of oils, to produce triacylglycerols with different properties. The molecular species
of natural triacylglycerols is not a random mixture of all possible isomers, but it shows greater
or lesser selectivity in the distribution of fatty acids between the sn-1 and sn-3 and the sn-2
positions (Table 7). This, as well as the overall fatty acid mixture, determines many of the tech-
nically important properties of the oil or fat, for example solid fat content and melting point.
Once subjected to interesterification with a chemical catalyst, the triacylglycerol becomes a
random mixture of molecular species. Lipase-catalyzed interesterification may alter the distri-
bution of molecular species in a more selective way.
Chemical interesterification [34, 35] is carried out at moderate temperatures (70–100 ∘ C),
with neat oils and a low concentration (<0.4%) of a base catalyst such as sodium methox-
ide or ethoxide or Na/K alloy. As the catalyst is destroyed by water and free fatty acids, the
oil must be carefully refined and dried before adding the catalyst. Reaction proceeds through
sequential fatty acid exchange reactions, following the formation of what is believed to be the
true catalyst, the alkali metal derivative of a diacylglycerol. There is no observed selectivity
for fatty acid or glycerol position, leading to a fully random product. The product composi-
tion can be controlled through directed interesterification at lower temperatures. Na/K alloy is
used as a catalyst as it is active at temperatures below 50 ∘ C and cooling the reaction mixture
causes high melting trisaturated triacylglycerols to crystallize out, altering the composition of
the liquid phase in which reaction occurs. The remaining liquid phase is randomized by fur-
ther reaction and high melting products continue to crystallize out, eventually leading to solid
and liquid products richer in trisaturated and triunsaturated species than the fully randomized
fat [35].
Interesterification is used to modify fat properties without recourse to partial hydrogena-
tion. Hardened fats produced by partial hydrogenation contain trans-isomers, which are now
regarded as undesirable by nutritionists and will be increasingly subject to product labeling
regulations. Liquid fats can be hardened by interesterification with fully saturated fats (either
stearin fractions or fully hydrogenated oils), raising the solid fat content without isomerizing
any of the fatty acids. The use of interesterification to produce margarine and spreads has
increased recently, particularly in Europe.
3.4. Lipase-Catalyzed Reactions

Lipases are enzymes that hydrolyze fatty acids from lipid species (e.g. triacylglycerols or
phospholipids) in vivo. A number of lipases, mainly of bacterial origin, are now available
immobilized onto a solid support for use as industrial-scale catalysts. Immobilized lipases
catalyze the whole range of ester exchange reactions described above (alcoholysis, acidolysis,
esterification) as well as hydrolysis. There are two significant differences between lipase and
chemically catalyzed reactions. First, lipase-catalyzed reactions take place at a lower temper-
ature and with fewer side reactions, leading to cleaner products: an environmentally friendly
alternative to some existing processes. Second, enzyme-catalyzed reactions are more selec-
tive, offering control overreactions not possible with a chemical catalyst. Selectivity may be
for fatty acids at different positions on the glycerol backbone (sn-1 and sn-3 rather than sn-2)
or for particular fatty acids, discriminating by double-bond position or chain length [36, 37].
The widely studied Lipozyme RM IM (Rhizomucor miehei lipase immobilized onto a weak
anion exchange resin) preferentially hydrolyzes short-chain acids relative to medium and long
chains from triacylglycerols. Hydrolysis at the sn-1 position is somewhat faster than at sn-3,
and hydrolysis at sn-2 is very slow [37].
Lipase-catalyzed reactions take place in the neat oil or in a nonpolar (usually hydrocarbon)
solvent. The efficiency depends on the amount of water, solvent (if present), temperature, and
ratio of reactants. A factorial approach can be used to optimize the conditions [38]. In inter-
esterification reactions, 1,3-specific enzymes give control over product composition that is not
possible using chemical catalysts. For example, starting with SOS and OOO, chemical inter-
esterification produces all eight possible isomers (see Table 7). Enzymatic interesterification
does not exchange fatty acids at the sn-2 position, and it will result in only two additional
molecular species, OOS and SOO. In more realistic situations, chemical and enzymatic inter-
esterification may produce the same or a similar number of molecular species, but in different
proportions [37].
Enzymatic interesterification has the most potential for high-value products such as con-
fectionery fats and nutritional products, for example cocoa butter equivalents prepared from
cheap and readily available starting materials. Acidolysis of palm mid fraction, rich in POP,
with stearic acid gives a cocoa butter equivalent rich in POSt and StOSt, through exchange at
the sn-1 and sn-3 positions while retaining the oleate at the sn-2 position. Tripalmitin treated
similarly with oleic acid gives products where the palmitate is retained at the sn-2 position,
whereas oleate is introduced at sn-1 and sn-3, producing a human milk fat substitute such as
Betapol. In practice, pure starting materials are not used. Feedstocks rich in tripalmitin and
oleic acid are reacted in a two step-process: alcoholysis to sn-2-monoacylglycerols followed
by esterification [39].
Both batch and fixed-bed reactors have been used and tested in the near ton scale [40]
for the production of high-value fats. This technology has now progressed to pilot produc-
tion, using a 1 m3 fixed-bed plug-in reactor containing the immobilized enzyme Lipozyme
TL IM [41]. Blends of palm oil or stearin with palm kernel or coconut oil are interesteri-
fied in less than one hour at 70 ∘ C, and no downstream processing is required as the enzyme
is retained in the reactor. This is a practical, lower energy alternative to hydrogenation and
chemical interesterification, free from the trans-isomer production of the former and more
selective and “natural” than the latter.
Lipases also discriminate between fatty acids with different double-bond positions. The
reaction of fatty acids with Δ4, Δ5, and Δ6 double bonds is significantly slower than Δ9 acids
when catalyzed by some enzymes. This is illustrated by some examples of attempts to con-
centrate Γ-linolenic acid (GLA; 18:3 6c9c12c) from borage oil. Hydrolysis of borage oil with
Candida rugosa lipase resulted in selective hydrolysis of the Δ9 acids (mainly 18:2) increasing
the amount of GLA in the remaining acylglycerols [42]. The efficiency of the enrichment was
influenced by the initial triacylglycerol composition and the extent of hydrolysis. Starting with
a borage oil containing 22% GLA, the upper limit of enrichment was to 46%, but higher values
resulted from repeated hydrolysis of the recovered acylglycerols. A two-step sequence involv-
ing both enzymatic hydrolysis and re-esterification achieved higher enrichment [43]. Nonse-
lective hydrolysis with Pseudomonas sp. lipase was optimized for high GLA recovery (93%).
Esterification with lauryl alcohol, using Rhizopus delemar lipase, discriminated strongly
against GLA, resulting in enrichment in the unesterified fatty acids from 22.5% to 70.2%
with a recovery efficiency of 75.1%. A 92.1% GLA concentrate, obtained by low-temperature
crystallization of borage oil fatty acids, was enriched to 99.1% by esterification with butanol,
catalyzed by Lipozyme IM-60 [44]. The overall recovery was 72.8%. The operating parameters
(alcohol, concentration, temperature, and solvent) were systematically investigated.
Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), Δ5 and Δ4 acids, respec-
tively, are discriminated against during lipase-catalyzed reactions and reaction of DHA may
be significantly slower than EPA. Alcoholysis of tuna oil ethyl esters with lauryl alcohol using
Rhizomucor miehei lipase enriches the DHA in the unreacted ethyl esters, whereas the con-
centration of EPA is simultaneously reduced [45]. A concentrate containing 60% DHA and
8.6% EPA was alcoholyzed with excess lauryl alcohol (1 : 7 mole ratio). The remaining ethyl
esters contained 93% DHA in 74% recovery, and EPA was reduced to 2.9%. Both nonre-
giospecific and sn-1,3-specific enzymes incorporate GLA into seal blubber and menhaden oil
(3 : 1 mole ratio of GLA to triacylglycerol) producing an oil rich in both n-3 and n-6 polyenes
[46]. The highest incorporation was with the nonspecific enzyme.
Ultrasound-assisted lipase-catalyzed hydrolysis activity has also been investigated in recent
years. Ultrasound is used to disrupt the aggregation of substrate molecules in the solvent,
making direct contact between enzyme and substrate easier. Ultrasound does not seem to
change the enantioselectivity of the lipase, nor does it amend its regioselectivity. Different
reaction conditions and different combinations of solvent used will influence the rate of lipase
hydrolysis reaction [47].
4. OXIDATION
The fatty acid alkyl chain is susceptible to oxidation both at double bonds and adjacent allylic
carbons. Free-radical and photooxidation at allylic carbons are responsible for the deteriora-
tion of unsaturated oils and fats, resulting in rancid flavors and reduced nutritional quality, but
they are also used deliberately to polymerize drying oils. Oxidation of double bonds is used
in oleochemical production either to cleave the alkyl chain or to introduce additional func-
tionality along the chain. Enzyme-catalyzed oxidation is the initial step in the production of
eicosanoids and jasmonates (biologically active metabolites in animals and plants respectively)
but is not discussed further here.
OXIDATION 15
4.1. Autoxidation and Photooxidation

Both autoxidation and photooxidation produce allylic hydroperoxides from unsaturated
centers.
CH CH CH2 + O2 CH CH CH(OHO)
During this process, the position and geometry of the double bond may change. The
hydroperoxide mixtures produced by autoxidation and photooxidation are not the same,
indicating that different mechanisms are involved. Free radical oxidation can be promoted
or inhibited. Deliberate promotion speeds the polymerization of drying oils, and strenuous
efforts are made to inhibit the onset of rancidity in edible oils. Frankel has recently reviewed
this topic in depth [48]; see also [1] for an extensive discussion of oxidation of food lipids.
4.1.1. Autoxidation Autoxidation is a free-radical chain reaction, involving a complex

series of reactions that initiate, propagate, and terminate the chain.
Initiation RH → R•
Propagation R• + O2 → ROO• Fast
ROO• + RH → ROOH + R• Rate determining
Termination R• , ROO• → stable products
The chain reaction is initiated by the abstraction of an allylic hydrogen to give an allylic
radical stabilized by delocalization over three or more carbons. The initiator is a free rad-
ical, most probably produced by decomposition of hydroperoxides already present or pro-
duced by photooxidation. The decomposition may be thermal, but it is more likely promoted
by traces of variable redox state metal ions. Autoxidation is characterized by an induction
period during which the concentration of free radicals increases until the autocatalytic propa-
gation steps become dominant. During the induction period, there is little increase in oxidation
products.
The first step of the propagation sequence is reaction of the allylic radical with molecular
oxygen, producing a peroxyl radical. This step is much faster than the subsequent abstraction
of another allylic hydrogen by the peroxyl radical, producing both an allylic hydroperox-
ide and a new allylic radical that continues the chain reaction. Hydrogen abstraction is the
rate-determining step and is, therefore, selective for the most readily abstracted hydrogen.
Methylene-interrupted dienes and polyenes, where the allylic radical can be delocalized over
five carbons, are oxidized faster than monoenes where the radical is delocalized over three
carbons (Figure 5).
•
(a) (b) •
Figure 5. Allylic radicals produced during autoxidation: (a) those from isolated double bonds are delo-
calized over three carbons and (b) those from methylene-interrupted dienes or polyenes are delocalized
over five carbons. The arrows show the site of attachment of O2 giving a peroxyl radical.
The chain reaction is terminated by reactions that remove radicals that would otherwise
produce more allylic radicals by hydrogen abstraction. Examples are the combination of two
hydroperoxyl radicals leading to nonradical products and molecular oxygen or reaction with
a free-radical scavenger (antioxidant) generating a more stable radical.
The rate of autoxidation generally increases with increasing unsaturation. Linoleate, as neat
methyl or ethyl ester, reacts approximately 40 times faster than oleate, and for higher polyenes,
the rate doubles for each additional double bond [49]. Trilinolein does not follow the same
kinetics as the simple esters and oxidizes somewhat faster. The medium also influences suscep-
tibility to oxidation, and these generalizations may not hold in emulsified systems (e.g. many
food formulations) where oxidation occurs at the interface between aqueous and fat phases
[50]. In aqueous micelles, EPA and DHA are unexpectedly stable [51], oxidizing much more
slowly than linoleate. In one experiment, over half the linoleate was oxidized within 50 hours
and ∼90% of EPA and DHA was still present after 2000 hours. The stability of the higher
polyenes is attributed to their tightly coiled configuration in the aqueous medium, making
attack by oxygen or free radicals more difficult.
Mechanistic studies of autoxidation have concentrated on methylene-interrupted fatty acids,
but many of the observations are valid for other compounds. Conjugated fatty acids such
as CLA also oxidize through an autocatalytic free radical reaction, with the predominant
hydroperoxide determined by the geometry of the conjugated diene system [52]. Other groups
with activated methylenes may be susceptible to oxidation, for example the ether methylenes
of ethoxylated alcohols used as surfactants [53].
4.1.2. Photooxidation Light, in the presence of oxygen, promotes oxidation of unsatu-

rated fatty acids. Ultraviolet radiation decomposes existing hydroperoxides, peroxides, and
carbonyl and other oxygen-containing compounds, producing radicals that initiate autoxi-
dation [49]. Photooxidation by longer wavelength near-ultraviolet or visible light requires a
sensitizer. Naturally present pigments such as chlorophyll, hematoporphyrins, and riboflavin
act as sensitizers as do dyes, including erythrosine and methylene blue. Light excites these
sensitizers to the triplet state that promotes oxidation by type I and type II mechanisms. Unlike
autoxidation, there is no induction period.
In type I photosensitized oxidation, the triplet state sensitizer abstracts a hydrogen or
electron from the unsaturated oil, producing radicals that initiate chain propagation as in
autoxidation. However, chain-breaking antioxidants do not stop this reaction as new radicals
are produced photochemically. In type II photooxidation, the energy of the triplet sensitizer
is transferred to molecular oxygen, converting it to its excited singlet state. Singlet oxygen
is highly electrophilic and reacts rapidly with olefins in an ene reaction, producing allylic
hydroperoxides with oxygen attached to one of the original olefinic carbons and the shifted
double bond now trans (Figure 6).
HOO
H
O O
Figure 6. Ene reaction between singlet oxygen and an olefinic bond. The hydroperoxide may be attached
to either of the initial double bond carbons.
OXIDATION 17
The ene reaction differs from free-radical oxidation, where oxygen attaches to an outer
carbon of the delocalized allylic radical (Figure 5), resulting in a different mixture of hydroper-
oxides. For example, photooxidation of linoleate produces four isomers: 9-OOH, 10t12c,
10-OOH, 8t12c, 12-OOH, 9c13t, and 13-OOH, 9c11t. The same 9- and 13-hydroperoxides
are produced by autoxidation, but the 10- and 12-hydroperoxides are only produced by
photooxidation.
Photooxidation is much faster than autoxidation; the reaction of linoleate with singlet
oxygen is approximately 1500 times faster than that with triplet oxygen [54]. There is less
difference in the rate of photooxidation between monoenes and polyenes than is seen in
autoxidation. The relative rates for oleate, linoleate, linolenate, and arachidonate are 1.0, 1.7,
2.6, and 3.1 [55, 56]. This contrasts with the 40-fold increase in rate of autoxidation between
oleate and linoleate.
4.1.3. Decomposition of Hydroperoxides Allylic hydroperoxides are reactive molecules

and decompose readily in a complex series of reactions, the course of which depends on the
medium and other conditions [1, 48]. Cleavage between the oxygens is energetically favored,
leading to alkoxy and hydroxyl radicals. Redox metal ions such as Fe2+ /Fe3+ and Cu+ /Cu2+
are particularly effective catalysts. The resulting radicals can initiate further autoxidation and
produce a number of stable products, many with undesirable nutritional and flavor proper-
ties (Figure 7). Products with the same chain length as the alkoxy radical include epoxides,
ketones, and hydroxy fatty acids. The significant products producing off-flavors are those
resulting from chain scission β to the alkoxy radical, producing shorter chain aldehydes and
R′ CH CH CH R′′
OOH
Keto
Epoxy
Fatty acids
•
OH + R′ CH CH CH R′′ Hydroxy
Dihydroxy
O•
Oligomers and polymers
A B
A R′′CHO + R′CH CH•
•
OH
R′CH CH OH R′CH2CHO
B R′CH CHCHO + R′′•
H•
R′′H
Figure 7. Decomposition reactions of allylic hydroperoxides.

hydrocarbons. Alkadienals have particularly low-odor thresholds and a few parts per billion
of nonadienals from n-3 fatty acids are responsible for a marked fishy taint even when other
signs of oxidation are absent [57].
There are a number of analytical measures of oxidative deterioration of oils and fats. The
most widely used are the peroxide value (PV) [19], which measures the hydroperoxide con-
tent by iodine titration and the anisidine value (AV) [19], which detects aldehydes by a color
reaction. As an oil suffers damage because of autoxidation, the hydroperoxide content, and
PV rise but do not do so indefinitely. As the hydroperoxides break down, the concentration
of aldehydes and AV increase. Oxidation is better assessed by a combination of PV and AV,
the Totox value (= 2 × PV + AV) being a better index of oxidation than either PV or AV alone.
Volatile products can be removed from oils by deodorization, but aldehydes attached to the car-
boxyl end of the chain remain part of the triacylglycerol (sometimes called “core” aldehydes)
and are indicators of previous oxidative damage.
4.1.4. Antioxidants Lipid oxidation is influenced by many factors: the medium, oxygen
concentration, temperature, light, degree of unsaturation, and metal ions among others. In the
presence of oxygen, oxidation cannot be entirely prevented nor can it be reversed, but it can
be inhibited, delaying the buildup of oxidized products to unacceptable levels. Antioxidants
can interact with several steps of free-radical or photooxidation. Their performance is medium
and concentration dependent and requires care as they can also act as prooxidants under some
conditions [58].
The most widely used antioxidants are free radical scavengers that remove reactive radi-
cals formed in the initiation and propagation steps of autoxidation. A number of natural or
synthetic phenols can compete, even at low concentrations, with lipid molecules as hydrogen
donors to hydroperoxyl and alkoxyl radicals, producing hydroperoxides and alcohols and an
unreactive radical. β-Carotene reacts with peroxyl radicals, producing a less-reactive radical.
These stabilized radicals do not initiate or propagate the chain reaction.
Tocopherols are phenolic antioxidants (Figure 8) naturally present in most plant oils. They
are concentrated in the distillate from physical refining, which results in a corresponding
OH
CH3 HO
HO HOOC
CH3 O
CH3
(a) (b)
OH OH OH
HO OH
HO O
O
OCH3 CH3 COOC3H7
(c) (d) (e) (f)
Figure 8. Natural antioxidants (a) α-tocopherol; (b) carnosic acid; (c) sesamol; synthetic antioxidants;
(d) butylated hydroxyanisole (BHA); (e) butylated hydroxytoluene (BHT); and (f) propyl gallate.
OXIDATION 19
decrease in the refined oil. Soybean distillate is a source of tocopherols for antioxidant formu-
lations. Carnosic acid (Figure 8) is isolated from rosemary and other herbs. Sesamol (Figure 8)
is a characteristic antioxidant of sesame oil, responsible for its high stability. Synthetic antiox-
idants are monocyclic phenols with highly branched substituents (Figure 8). In all of these
compounds, the radicals formed by abstraction of the phenolic hydrogen are highly delocalized
and unreactive. The antioxidant action of free-radical scavengers is sacrificial, delaying oxi-
dation until the antioxidant is used up. Oxidized tocopherols may be regenerated by ascorbic
acid, extending their effective life while keeping their concentration below prooxidant levels.
Plant oils often contain essential oils of intense aroma. Organic molecules of different
functional groups found in these essential oils have high antioxidant and antiradical prop-
erties. In different models of oxidation reactions, there is an optimal composition of essential
oils, which maximizes antiradical and antioxidant properties. For example, essential oils with
monoterpene and their derivatives as the main component and relatively low phenol content,
have high antiradical activity. In systems of hexanal oxidation, essential oils with the highest
phenol content have high antioxidant activity. In the β-carotene model system, essential oils
containing carvacrol are efficient antioxidants. Essential oils containing terpinenes, but not
phenols, have the lowest antiradical and antioxidant activity [59].
Photooxidation is not inhibited by free-radical scavengers. Natural pigments that act as
sensitizers may be reduced during refining, increasing stability. Singlet oxygen and excited
state sensitizers can be deactivated either by competitive reaction or physical energy transfer,
for example, to β-carotene. Tocopherols and some amines also act as singlet oxygen quenchers
through physical energy transfer.
Redox metal ions, particularly iron and copper, react with hydroperoxides, initiating further
autoxidation and producing undesirable decomposition products. Complete removal of these
metal ions is not possible, but steps can be taken to reduce their effect. Chelating agents such
as ethylenediaminetetraacetic acid (EDTA), citric acid, phosphate, and polyphosphates may
reduce the effective metal ion concentration. Their efficacy depends on pH, and they may
also show prooxidant activity. The role of metal ions in hydroperoxide decomposition in food
emulsions has been reviewed recently [60].
4.2. Epoxidation
Epoxides are produced by the reaction of double bonds with peracids. This proceeds by a
concerted mechanism, giving cis stereospecific addition (Figure 9) [61]. Thus, a cis olefin
leads to a cis epoxide and a trans olefin to a trans epoxide. The order of reactivity of some
peracids is m-chloroperbenzoic > performic > perbenzoic > peracetic; electron-withdrawing
groups promote the reaction. The carboxylic acid produced is a stronger acid than the strongly
hydrogen-bonded peracid and may lead to subsequent ring-opening reactions especially in
the case of formic acid. Small scale reactions are carried out with m-chloroperbenzoic acid in
R H R H O R H H
H O H O
O R′′ O +
O O
R′ H O R′′ R′ H O R′ H O R′′
Figure 9. Epoxidation mechanism proposed by Bartlett [61]. The cis-olefin gives rise to a cis-epoxide.
a halocarbon or aromatic solvent, in the presence of bicarbonate to neutralize the carboxylic

acid as it is formed [62, 63].
Oils, mainly soybean but also linseed, are epoxidized on an industrial scale (100 000 tons
per year) as stabilizers and plasticizers for Polyvinyl chloride (PVC). The reactive epoxide
groups scavenge HCl produced by the degradation of the polymer. Epoxidation is carried out
with performic or peracetic acid produced in situ from formic or acetic acid and high strength
hydrogen peroxide (70% w/w). Peracids are unstable, and the reaction is exothermic. The
concentration of peracid is kept low by using a low concentration of the carboxylic acid either
in the neat oil or in a hydrocarbon solvent. The carboxylic acid is regenerated after epoxidation.
Complete epoxidation is not achieved as in the acidic medium ring-opening reactions occur
producing dihydroxy and hydroxy carboxylates as by-products.
Recent studies have attempted to improve the efficiency of epoxidation under milder con-
ditions that minimize the formation of by-products. Chemo-enzymatic epoxidation uses the
immobilized lipase from Candida antartica (Novozym 435) [64] to catalyze the conversion
of fatty acids to peracids with 60% hydrogen peroxide. The fatty acid is then self-epoxidized
in an intermolecular reaction. The lipase is remarkably stable under the reaction conditions
and can be recovered and reused 15 times without loss of activity. Competitive lipolysis
of triacylglycerols is inhibited by small amounts of fatty acid, allowing the reaction to be
carried out on intact oils [65]. Rapeseed oil with 5% of rapeseed fatty acids was converted
to epoxidized rapeseed oil in 91% yield with no hydroxy by-products. Linseed oil was
epoxidized in 80% yield. Methyl esters are also epoxidized without hydrolysis under these
conditions.
Methyltrioxorhenium (MTO) catalyzes direct epoxidation by hydrogen peroxide. The
reaction is carried out in pyridine, avoiding acidic conditions detrimental to high epoxide
yield and uses less concentrated hydrogen peroxide (30%) than other methods [66]. This
method epoxidized soybean and metathesized (see Section 7.4) soybean oil in high yield
[67]. The epoxidized metathesized oil was more stable to polymerization than that produced
using m-chloroperbenzoic acid, presumably because it was free of acidic impurities. These
and other novel approaches to epoxidation have recently been reviewed [4, 68, 69]. None has
yet found industrial application.
Epoxides are reactive and readily ring open in acid, following protonation of the epoxy
oxygen (Figure 10). This is a route to diols (see Section 4.3), polyols used in polymer produc-
tion and a range of α-hydroxy compounds. Ring opening of methylene-interrupted diepoxides
leads to five and six membered ring ethers through neighboring group participation [7].
4.3. Hydroxylation
Double bonds are converted to monohydroxy derivatives by acid-catalyzed addition of car-
boxylic acids, followed by hydrolysis. The carbocation intermediate is prone to rearrangement,
leading to a mixture of positional isomers. Hydroboration with borane: 1,4-oxathiane followed
by alkaline hydrolysis a regioselective reaction [70] has been used to prepare hydroxy fatty
acids as GC-MS standards in high yield [71].
Hydroxylation reactions leading to diols have much in common with epoxidation and oxida-
tive cleavage reactions (see Section 4.4), the end product depending on the strength of the
oxidizing agent. Dilute alkaline permanganate or osmium tetroxide react through cyclic inter-
mediates resulting from cis addition of the reagent giving an erythro diol. Ring-opening epox-
ides with acid is a trans addition, leading to a threo product (Figure 10).
OXIDATION 21
(1)
O O
i Mn HO OH
O O Erythro
ii
iii OAc iv OH
(2)
O HO HO
Threo
Figure 10. Stereochemistry of hydroxylation reactions: (1) with dilute alkaline permanganate and
(2) through epoxide ring opening. (i) KMnO4 , NaOH; (ii) m-chloroperbenzoic acid, NaHCO3 , CH2 Cl2 ;
(iii) CH3 COOH; (iv) base-catalyzed hydrolysis.
An oxygen bridged manganese complex was recently reported to catalyze double-bond

oxidation by hydrogen peroxide leading to a mixture of epoxide, cis-diol, and hydroxy ketone
products [72]. This is an interesting model reaction for the efficient use of hydrogen peroxide
as a cheap hydroxylating agent if the selectivity can be improved. A number of microorgan-
isms are reported to produce a range of novel di- and trihydroxy fatty acids and are being
investigated as potential biocatalysts [73].
4.4. Oxidative Cleavage

Double bonds are cleaved by a number of oxidizing agents, converting the olefinic carbons
to carboxylic acids, aldehydes, or alcohols. Fatty acids give a monofunctional product from
the methyl end and a difunctional product from the carboxyl end (along with low-molecular-
weight products from methylene-interrupted systems).
Although now largely superseded by GC and GC-MS methods for structure determination,
oxidative cleavage with ozone or permanganate/periodate and identification of the resulting
products is a powerful method for double-bond location, particularly for monoenes [25].
Reaction with alkaline permanganate/periodate proceeds through the diol resulting from
reaction with dilute permanganate (see Section 4.3). The diol is split into two aldehydes
by reaction with periodate, and the aldehydes are subsequently oxidized to carboxylic acids
by permanganate. Alternatively, diols derived from double bonds are cleaved to aldehydes by
lead tetraacetate or periodate.
Ozone reacts directly with double bonds under mild conditions and is the preferred degrada-
tive method for double-bond location [25]. The reaction occurs in several steps [72], starting
with a 1,3-dipolar cycloaddition (Figure 11). The addition product decomposes rapidly into
an aldehyde and a carbonyl oxide. In the absence of solvent or in nonparticipating solvents,
these recombine forming a relatively stable 1,2,4-trioxolane or ozonide. The separation into
aldehyde and carbonyl oxide during this rearrangement is supported by the production of six
ozonide species from unsymmetrical olefins. Ozonides can be converted to a number of stable
products; oxidation yields carboxylic acids, mild reduction gives aldehydes, and treatment with
nickel and ammonia gives amines providing useful synthetic routes to difunctional compounds
from fatty acids (e.g. Furniss et al. [74]). In a carboxylic acid or alcohol solvent, the carbonyl
oxide reacts with the solvent producing mainly acyloxy or alkoxyhydroperoxides, respectively,
H H H
H H
O H O H
R R′ R′ H
R + R′
O O
O O– O R O O– R O O R′
O
+ (1) (2)
H H OR′′
+ + R′′OH
R O O– R O OH
(1) (3)
Figure 11. Ozonolysis reaction mechanism. In nonparticipating solvents, the carbonyl oxide (1) and alde-
hyde recombine to give the moderately stable ozonide (2). Hydroperoxides (3) are formed in protic
solvents, and R′′ can be alkyl or acyl.
along with other more complex products [75]. These hydroperoxides are oxidized or reduced
to the same products as the ozonides.
Ozonolysis is the only oxidative cleavage that is used industrially. Around 10 000 tons per
year of azelaic acid (nonane-1, 9-dioic acid) are produced along with pelargonic acid (nonanoic
acid) by ozonolysis of oleic acid. Azelaic acid is used for polymer production and is not readily
available from petrochemical sources. Other dibasic acids potentially available by this route are
brassylic (tridecane-1,13-dioc) and adipic (hexane-1,6-dioic) acids from erucic (22:1 13c) and
petroselenic (18:1 6c) acids, respectively. High-purity monoenes are required as feedstock to
avoid excessive ozone consumption and by-products. Ozonolysis is a clean reaction, carried
out at low temperatures without catalyst. However, ozone is toxic and unstable, as are the
intermediates. Industrial-scale ozonolysis is carried out in pelargonic acid run countercurrent
to ozone at 25–45 ∘ C followed by decomposition at 60–100 ∘ C in excess oxygen [76]. Ozone
must be generated continuously on-site by electrical discharge in air, and ozone production is
the limiting factor for large-scale production [77].
Ruthenium oxide (RuO4 ) catalyzes oxidative cleavage of oleic acid to pelargonic and aze-
laic acids efficiently in the presence of NaOCl as an oxygen donor to regenerate Ru(VIII) [78].
However, the production of halogen salt by-products makes this impractical for large-scale
production. Hydrogen peroxide and peracetic acid are cheaper and more environmentally
benign oxidants, the by-product from reaction or regeneration of peracid being water, but give
very low yields with RuO4 . Ruthenium(III) acetylacetonate (Ru(acac)3 ) with peracetic acid or
Re2 O7 with hydrogen peroxide give moderate yields with internal double bonds, but ∼80%
conversion with terminal olefins. Terminal olefins, produced from fatty acids with an internal
double bond by metathesis with ethylene, are converted to dibasic acids without concomitant
production of monobasic acids. Diols produced by hydroxylation are cleaved by Re2 O7 with
hydrogen peroxide to di- and monobasic acids (Figure 12). These reactions offer an alterna-
tive to ozonolysis for the production of dibasic acids, but they have still to be optimized for
industrial application [78, 79].
5. REDUCTION
Both carbon–carbon double bonds and the carboxyl group of fatty acids can be reduced, either
together or separately depending on the reaction conditions. Catalytic reduction is an important
REDUCTION 23
COOR
H2C=CH2
metathesis
COOR
HO OH
RuO2/NaOCl
+
H2O2
Re2O7 COOR
CH3CO3H/Ru(acac)3
or
HOOC COOR
H2O2/Re2O7
+
COOH HOOC COOR
Figure 12. Alternative oxidative cleavage reactions.
industrial route to hardened fats, fatty alcohols, and fatty amines, using well-established tech-
nologies.
5.1. Hydrogenation of Double Bonds

Transition metals such as Co, Ni, Cu, Ru, Pd, and Pt catalyze hydrogenation of double
bonds. Palladium on charcoal or Adam’s catalyst (platinum oxide) promotes saturation of
fatty acids at ambient temperature and hydrogen pressure. Hydrogenation is accompanied by
exchange and movement of hydrogen atoms along the chain in the region of the double bonds,
demonstrated by the large number of isotopomers formed on deuteration. Homogeneous
deuteration with Wilkinson’s catalyst (tris (triphenylphosphine)rhodium(I) chloride) proceeds
without hydrogen movement or exchange [80] and in conjunction with GC-MS analysis
is used to locate double bonds. Partial hydrogenation with hydrazine does not isomerize
unreacted double bonds and is useful for structural analysis of polyenes and was recently
used to examine long-chain metabolites of CLA [81].
5.2. Catalytic Partial Hydrogenation

Partial hydrogenation reduces the polyene content of oils while maintaining or increasing the
monoene content. Reduction of double bonds is accompanied by a variable degree of cis-to
trans-isomerization. “Brush” hydrogenation of soybean or rape oil reduces linolenic content,
improving oxidative stability, whereas more extensive hydrogenation increases solid fat con-
tent, producing “hardened” fats for spreads and shortenings. Partial hydrogenation of fish oil
can produce biofuel of excellent suitability as blending component for fossil diesel fuel [82].
Partial hydrogenation has been used for the past century, in margarine production and remains
an important process for edible fat modification despite concerns about adverse nutritional
properties of trans-fatty acids. There are recent reviews of the mechanism [83, 84] and tech-
nology [85]. The concerns about adverse nutritional properties of trans-fatty acids encouraged
the development of partial hydrogenation reactors that produce minimal amount of trans-fatty
acids [86]. In recent years, there is an increasing trend to replace partial hydrogenation in
lipid processing with interesterification, especially in edible lipid to prevent the adverse health
effects of trans-fat consumption [87].
A number of uncertainties remain about the mechanism of the reaction and the factors
controlling selectivity between polyenes and monoenes, and the balance between hydrogena-
tion and isomerization. Hydrogenation is a three-phase reaction among liquid oil, gaseous
hydrogen, and solid catalysts carried out as a batch process in autoclaves to maintain consistent
products. Temperature, hydrogen pressure, amount and formulation of catalyst, and agitation
are all carefully controlled. Supported nickel is invariably used as catalyst. Although other
catalysts are equally or more effective, nickel has widespread acceptance from long use, ease
of removal, and low cost. Unremoved traces of other metals such as copper might also reduce
the oxidative stability of the product.
The reaction mechanism must account for the selectivity of the reaction (polyenes reacting
faster than monoenes) and the production of trans-monoenes. Hydrogen addition is in two
steps with a semihydrogenated intermediate. Addition of the first hydrogen is reversible,
regenerating a double bond with potentially altered position or geometry. Addition of a
second hydrogen irreversibly produces a saturated bond (Figure 13). Dijkstra [84] proposed
that for dienes, the formation of the semihydrogenated intermediate is rate determining and
hydrogen concentration dependent, whereas for the conversion of monoene to saturate, the
rate-determining and hydrogen concentration-dependent step is the addition of the second
hydrogen. At low dissolved hydrogen concentrations, isomerization of monoenes is favored
oversaturation, allowing control of the product composition by hydrogen pressure, agitation,
and reaction time.
Copper catalysts show different selectivity compared with nickel. Copper only catalyzes
hydrogenation of methylene-interrupted systems, showing high selectivity for polyenes and
Catalyst H
(1)
H H
D∗ + H
D + H DH +H
Slow
M
M∗
M + H MH
+H
Slow S
Figure 13. Partial hydrogenation. The partially hydrogenated intermediate (1) may lead to cis or trans
unsaturated or saturated products. D, diene; M, monoene; S, saturate; * potentially isomerized. Formation
of M* is favored at a low hydrogen concentration.
PRODUCTION OF SURFACE-ACTIVE COMPOUNDS AND OLEOCHEMICALS 25
no reaction with oleate or other monoenes produced by reduction of polyenes. The first step is
production of conjugated dienes that are the species hydrogenated. Dijkstra recently reassessed
this reaction, suggesting removal of an allylic hydrogen as the first step in production of the
conjugated diene [88].
5.3. Production of Fatty Alcohols

Triacylglycerols, fatty acids, and esters can be reduced to aldehydes, alcohols, or hydrocar-
bons, the main application being the production of fatty alcohols. On a small scale, lithium
aluminum hydride (in excess of stochiometric requirement) is a convenient reducing agent
for the carboxyl group without affecting polyunsaturated chains. Industrially, catalytic hydro-
genation is used and has been reviewed [89, 90].
Long-chain alcohols are produced from both oleochemical and petrochemical sources.
Oils and fats provide straight-chain lengths not readily available otherwise and the possibility
of unsaturated chains. The main feedstocks are coconut and palm kernel oil for C12 –C14
alcohols and technical grades of tallow and palm oil for C16 –C18 alcohols. The preferred
starting material for catalytic hydrogenation is methyl ester. Fatty acids are corrosive and
need harsh reaction conditions, leading to unwanted by-products. Reduction of intact oils
leads to loss of glycerol, a valuable by-product, through over-reduction to propanediol and
propanol, as well as excessive hydrogen and catalyst consumption. Methyl esters are reduced
to saturated alcohols with copper chromite catalyst (∼2%) at 250–300 ∘ C and 25–30 MPa
(250–300 bar) hydrogen in a suspension system or at 200–250 ∘ C with a fixed-bed catalyst.
There is an effort to develop environmentally friendly nonchrome catalyst for the process
[91]. The methanol produced is recycled for methyl ester production. Zinc-based catalysts
do not hydrogenate double bonds and are used to produce unsaturated alcohols such as
oleyl alcohol. Increasing energy costs and environmental concerns have led to the recent
development of the microbio-production of fatty-acid-derived chemicals from plant-derived
biomasses such as hemicellulose [92].
6. PRODUCTION OF SURFACE-ACTIVE COMPOUNDS AND OLEOCHEMICALS
One of the main nonfood use of oils and fats is the production of surfactants. The amphiphilic
properties of fatty acids, exploited for centuries in the use of soaps, can be modified by
changing the carboxyl group into other hydrophilic groupings, giving anionic, cationic,
amphoteric, and nonionic surfactants. There is also scope for functionalizing the aliphatic
chain, but this has not been widely used commercially. The chain length of the feed stock,
C12 –C14 from lauric oils, C22 from high erucic rape and fish oils, and C16 –C18 from most
other sources, can be used to modify solubility. The main starting materials for surfactant
production are fatty acids and alcohols with a range of N-containing derivatives produced
through amides and amines. Surfactants of oleochemical origin may biodegrade better
than petrochemical products, giving an environmental benefit in addition to being derived
from renewable resources. Recently, surfactants have been produced from fully renewable
resources. Oleochemical surfactant production has been reviewed [93–97]. From the early
mention of producing surfactants by microorganism, the research in this technology has come
a long way. However, their application in large scale is limited by high cost. As environmental
concerns have become increasingly urgent, more efforts have been directed to the development
of environmentally friendly production technologies [98].
6.1. Nitrogen-Containing Compounds

The presence of nitrogen, either in a neutral or cationic group, gives surfactant properties
that are not easily produced with other compounds. A diverse range of nitrogen-containing
compounds is produced, for which the starting point is an amide or amine. Amides are formed
by direct reaction of the fatty acid and ammonia at 180–200 ∘ C and 0.3–0.7 MPa (3–7 bar),
through dehydration of the initially formed salt. Long-chain amides, e.g. erucamide, are the
principle industrial products, used as polythene film additives.
Amines are produced from fatty acids in a reaction sequence in which the nitrile is an
intermediate. Nitriles are produced by reaction of the fatty acid with ammonia, giving the
amide that is dehydrated in situ at 280–360 ∘ C in the liquid phase on a zinc oxide, manganese
acetate, or alumina catalyst. Lower temperature and longer reaction times are used with unsatu-
rated fatty acids to avoid polymerization. Hydrogenation with nickel or cobalt catalyst reduces
the nitrile to amines via the aldimine (RCH NH). Depending on the reaction conditions, the
aldimine reacts with hydrogen or primary or secondary amines, giving primary, secondary, or
tertiary amines, respectively, as the major product. Primary amines are produced at 120–180 ∘ C
and 2–4 MPa (20–40 bar); higher temperature and lower pressure favors the production of
secondary and tertiary amines with a symmetrical substitution at the nitrogen. The long-chain
composition closely reflects the fatty acid composition of the feedstock, although hydrogena-
tion conditions can be adjusted to hydrogenate the alkyl chains or induce cis–trans-isomerism.
The more widely used unsymmetrical tertiary amines are produced from primary amines,
amides, or alcohols (Table 8). Reactions converting amines to other surface-active derivatives
and for the preparation of other nitrogen-containing compounds are shown in Table 8. These
have appeared in several reviews [2, 94, 96, 99, 100].
N CH2
RC
N CH2
CH2CH2NH2
TABLE 8. Routes to nitrogen-containing surfactants.
Product
RCH2 NH2 + CH2 O → (reduction) → RCH2 NMe2 Tertiary amine

RCH2 CONMe2 → (reduction) → RCH2 NMe2 Tertiary amine
RCH2 OH + Me2 NH → (catalytic hydrogenation) → RCH2 NMe2 Tertiary amine
ROH + CH2 CHCN → RO(CH2 )2 CN → (reduction) → RO(CH2 )3 NH2 Etheramine
RNH2 + CH2 CHCN → RNH(CH2 )2 CN → (reduction) → RNH(CH2 )3 NH2 Diamine
RNH(CH2 )3 NH2 + CH2 CHCN → RNH(CH2 )3 NH(CH2 )2 CN → (reduction) → Triamine
RNH(CH2 )3 NH(CH2 )3 NH2
RO(CH2 )3 NH2 + 2nCH2 (O)CH2 → RO(CH2 )3 N((CH2 CH2 O)n H)2 Ethoxylated etheramine
RNH(CH2 )3 NH2 + 2nCH2 (O)CH2 → RNH(CH2 )3 N(CH2 CH2 O)n H)2 Ethoxylated diamine
RNH2 + nCH2 (O)CH2 → H(OCH2 CH2 )n N(R)(CH2 CH2 O)n H Ethoxylated amine
RN(Me)2 + (H2 O2 ) → RN+ (Me)2 O− Amine oxide
RN(Me)2 + (MeCl or Me2 SO4 ) → RN+ (Me)3 X− Quaternary amine
R3 N + (benzyl chloride) → R3 N+ Bz X− Quaternary amine
RCOOH + NH2 (CH2 )2 NH(CH2 )2 NH2 → 4 Imidazoline
2RCOOH + (HOCH2 CH2 )2 NCH3 → (RCOOCH2 CH2 )2 NCH3 + H2 O Ester amine
PRODUCTION OF SURFACE-ACTIVE COMPOUNDS AND OLEOCHEMICALS 27
6.2. Ethoxylation
Long-chain molecules with active hydrogen (alcohols, amines, and amides) react as nucle-
ophiles with ethylene oxide usually with a basic catalyst. The product has a hydroxyl group
that can react with further ethylene oxide, leading to polyoxyethylene products with a range
of molecular weights. The average number of ethylene oxide molecules added depends on the
reaction conditions and can be adjusted to alter the solubility and surfactant properties of the
product.
ROH + nC2 H4 O → RO(C2 H4 O)n H
Typical reaction conditions are 120–200 ∘ C and pressures of 0.2–0.8 MPa (2–8 bar) with
potassium hydroxide or sodium alcoholates as catalyst [95]. In the reaction with primary
amines, both active hydrogens are replaced before further ethylene oxide addition leading
to dipolyoxyethylene derivatives. Polyoxyethylenes have a terminal hydroxyl that may be
further functionalized under conditions that do not damage the ether linkages, for example
sulfation.
6.3. Sulfation
Sulfate esters of alcohols or polyoxyethylene alcohols are prepared by reaction with sulfur
trioxide in continuous falling-film plants, immediately followed by neutralization with sodium
hydroxide to give the sodium salt [93].
ROH + SO3 → ROSO3 H

ROSO3 H + NaOH → ROSO3 Na + H2 O
Alcohol sulfates are not stable in acid and are used in alkaline formulations. C12 –C16
alcohol sulfates have excellent detergency, high foam, and good wetting properties. Alcohol
sulfates are fully biodegradable under aerobic and anaerobic conditions and compete in per-
formance with petrochemical-derived linear alkylbenzene sulfonates (LABS).
Mono- and diacylglycerols are starting materials for sulfate ester surfactants that can be
prepared directly from triacylglycerols without reduction to the fatty alcohol. Cocomonoacyl-
glycerol sulfates, used in cosmetic formulations, are produced in a solvent-free process [101].
Glycerolysis of coconut oil (mole ratio of glycerol to oil of 2 : 1) gives the raw material for
sulfatization, predominantly mono- and diacylglycerols. Membrane filtration is used to desalt
the product.
6.4. 𝛂-Sulfonates
The methylene adjacent to the carboxyl group is sufficiently activated to react with sulfur
trioxide, giving α-sulfonate products. As allylic methylenes are similarly activated, the reac-
tion is usually carried out with saturated starting materials. The complex reaction involves
two moles of sulfur trioxide, giving a disulfonate intermediate that reacts with methyl ester
to give the α-sulfonate ester, or on treatment with sodium hydroxide the disodium salt [93].
α-Sulfonates have low toxicity and are fully biodegradable.
RCH2 COOH3 + 2SO3 → RCH(SO3 H)COOSO2 OCH3

RCH(SO3 H)COOSO2 OCH3 + RCH2 COOCH3 → 2RCH(SO3 H)COOCH3
OH
O
OH O
HO
OH O
OH O
HO
OH
y
Figure 14. Alkyl polyglycoside. Degree of polymerization = y + 1.
6.5. Carbohydrate-Based Surfactants

Carbohydrates and related polyols (as well as amino acids) have attracted attention as the
hydrophilic component of nonionic surfactants, particularly as a benign alternative to manu-
facture using ethylene oxide. Sucrose, glucose, and sorbitol (from hydrogenation of glucose)
are available in quantity from renewable resources. Although sorbitol esters have been in use
for many years, large-scale synthesis of sugar esters remains difficult because of the similar
reactivity of all the carbohydrate hydroxyls, leading to many molecular species in the product.
Further difficulties are the insolubility and charring of the carbohydrate in the reaction medium.
A more controllable reaction is that between long-chain alcohols and glucose, giving alkyl
polyglycosides with the fatty alcohol ether linked only to position C-1 on the glucose ring. Fur-
ther glucose units are also joined through ether links. Both the alcohol and glucose can be pro-
duced from renewable resources (oils and fats and starch, respectively), and the reaction can be
carried out in a solvent-free system. In commercial production, glucose is suspended in excess
alcohol and reacted at 100–120 ∘ C with a sulfonic acid catalyst. The product has an average
degree of polymerization of 1.2–1.7 glucose units per molecule (Figure 14) and is nonirritant
and fully biodegradable [101–104]. Alkyl polyglycoside production is currently ∼100 000 tons
per year, which is used in detergent formulations in place of petrochemical-derived prod-
ucts. Carbohydrate-based surfactants show promising results as photocontrolable inhibitors
of ice recrystallization. This technology has a significant application in medical science since
carbohydrate-based surfactants can be developed into cryoprotectants for the storage of bio-
logical substances such as red blood cells at sub-zero temperatures [105].
6.6. Dimers and Estolides

A number of different dimers and oligomers are produced from fatty acids and alcohols. These
are branched-chain compounds with significantly lower melting points than straight-chain
structures of similar molecular weight. Fully saturated dimers have excellent oxidative stabil-
ity. This and their extended liquid range are exploited in their use as lubricants and cosmetic
additives. Polyfunctional dimers are used in polymer formulations.
Dimer acids. Dimer acids are produced by heating monoene or diene fatty acids (e.g. tall
oil acids, a by-product of wood pulping) with a cationic clay catalyst [106]. Typical conditions
are 4% montmorillonite at 230 ∘ C for four to eight hours. After distillation, the product is a
complex mixture of acyclic, cyclic, and bicyclic dimers along with some trimer. Dimer acids
are dibasic and react with diamines and triamines to give polyamides. Imidazole derivatives
are used as corrosion inhibitors and esters as lubricants.
MODIFYING FATTY ACID STRUCTURE 29
OH
(a)
13
O O
13
O O
n
OH
(b) 13
Figure 15. (a) Guerbet alcohol from lauryl alcohol (12:0); (b) estolide from meadowfoam acids (20:1 5c).
Guerbet compounds. Guerbet alcohols have been known for over a century and are pro-
duced by the alkali catalyzed dimerization of aliphatic alcohols with accompanying loss of
water. Typical reaction conditions are heating at 200–300 ∘ C with potassium hydroxide in
the presence of transition metal compounds to catalyze the intermediate reduction step. Dehy-
drogenation of the alcohol to the aldehyde is followed by aldol condensation and rehydrogena-
tion to give the branched-chain alcohol (Figure 15a).
The alcohols can be oxidized to the corresponding acids. Guerbet alcohols, acids, their
esters, sulfates, and ether sulfates are used as lubricants, cosmetic additives, and surfactants.
Their synthesis, characterization, and applications have been reviewed [107].
Estolides. Estolides are ester-linked branched-chain compounds. They are normally
produced under harsh conditions similar to those used to produce dimer acids, but with the
addition of around 10% water. Mono- and polyestolides are used as lubricants, greases, and
surfactants, and in cosmetic, ink, and plastic formulations. Estolides biodegrade rapidly and
completely, at rates comparable with the vegetable oils and fatty acids from which they are
derived [108], making them environmentally benign products. The Δ5 monoene acids in
meadowfoam oil form estolides under mild acid catalysis, neighboring group participation by
the carboxyl group facilitating the reaction (Figure 15b) [109]. The product from meadow-
foam acids shows higher regioselectivity than that from acids with mid-chain olefins where
the double bond is further from the carboxyl group. Estolides from mid-chain olefins have
significantly lower pour points than the corresponding fatty acids or triacylglycerols, but
those from meadowfoam acids show little difference.
7. MODIFYING FATTY ACID STRUCTURE
Isomerization and conjugation change the properties of natural methylene-interrupted fatty

acids, leading to new applications and potential added value. Chain shortening or extension
produces fatty acids not readily isolated from natural sources and is also used to introduce
radioactive or stable isotope labels. Metathesis provides a flexible method for modifying the
alkyl chain.
7.1. Isomerization
Trans-isomers of fatty acids are more stable thermodynamically than cis-isomers, because of
reduced steric crowding; the equilibrium ratio is approximately 4 : 1 trans/cis. There is a
considerable energy barrier to interconversion (∼125 kJ mole−1 ). Before the attached groups
can rotate about the double bond, it has to be weakened by coordination to a catalyst, high
temperature, or temporary conversion to a single bond through addition and elimination
reactions. Chemical isomerization agents leading to an equilibrium mixture include sele-
nium (through a Π-complex) and nitrogen oxides or thiols (through free-radical addition/
elimination).
Cis- to trans-isomerization accompanies partial hydrogenation (see Section 5.2) and may
be exploited to raise the melting point. Unwanted isomerization occurs during physical
refining at temperatures above 250 ∘ C. More unsaturated acids isomerize faster, making
linolenic containing seed oils (e.g. soybean and canola) particularly vulnerable. Conditions
for deodorizing rape oil without isomerization have been optimized following a detailed study
and development of a model of the isomerization kinetics [110].
7.2. Conjugation
Heating with alkali has long been used to produce conjugated drying oils for paints and
varnishes. The anion resulting from removal of a bis-allylic methylene rearranges through
migration and isomerization, giving a cis, trans-conjugated system (Figure 16). Thus, linoleic
acid (18:2 9c12c) gives both 9c11t and 10t12c isomers, whereas trienes give a mixture of
partially and fully conjugated isomers depending on whether the middle or an outer double
bond migrates first. Under the harsh conditions used to prepare drying oils (aqueous alkali at
∼230 ∘ C), a complex mixture of isomers is eventually formed, but under controlled conditions
(e.g. KOH in propylene glycol at 150 ∘ C), a mixture containing only the 9c11t and 10t12c
CLA isomers is produced [111]. This product and individual isomers prepared from the
mixture are used as nutritional supplements.
Thermal isomerization of linoleic acid produces a conjugated isomer mixture that does
not contain all possible cis- and trans-isomers. The absence of the 8c10t and 11t13c isomers
suggests a concerted pericyclic mechanism that limits the geometrical possibilities for
OH– –
+
–
–
H2O
Figure 16. Alkali-induced conjugation of methylene-interrupted olefins.

MODIFYING FATTY ACID STRUCTURE 31
the rearranged double bonds [112]. [RhCl(C8 H14 )2 ]2 in the presence of (p-CH3 C6 H4 )3 P
and SnCl2 •2H2 O is an efficient homogeneous catalyst for the conjugation of linoleic acid,
producing conjugated soybean oil with exceptional drying properties and high solvent
resistance in high yield [113].
7.3. Chain Shortening and Extension

Fatty acids can be labeled at the carboxyl carbon with 13 C or 14 C by chain shortening fol-
lowed by chain extension with labeled carbon. Chain shortening to the nor-halide using the
Hunsdieker reaction (decarboxylation of fatty acid silver salts in the presence of halogens) is
only suitable for saturated acids, but unsaturation is not altered using the alternative devel-
oped by Barton employing N-hydroxy-pyridine-2-thione in a halocarbon solvent [114]. Chain
extension with labeled cyanide followed by hydrolysis or reaction of the derived Grignard
reagent with labeled carbon dioxide gives the labeled fatty acid. The Barton decarboxylation
was recently used to prepare gram quantities of 1-[13 C]-linoleic and 1-[13 C]-linolenic acids
for metabolic studies [115].
Two-carbon chain extension at the carboxyl end, mimicking biosynthesis, uses the malonic
ester route [116]. After reduction of the carboxyl to an alcohol, the readily displaced mesylate
is prepared and reacted with sodium diethylmalonate. Saponification and decarboxylation give
the chain extended product in high yield. This is an efficient route to C20 polyenes, not easily
isolated from natural sources, starting from readily available C18 sources.
Metathesis (see Section 7.4) provides a flexible route to longer and shorter chains after
reaction at a (usually monoene) double bond.
7.4. Olefin Metathesis

Olefin metathesis is the catalytic exchange of groups attached to a double bond. It presents a
number of interesting possibilities for modifying the alkyl chain of fatty acids (Figure 17).
H H Catalyst H H H H
+
R R′ R R R′ R′
R R R
LnM C LnM L nM
+
R′ R′′ R′ R′′ R′ R′′
PR3
Ph Mes N N Mes
Cl Cl
Ru Ph Ru
Cl Cl
PR3 PCy Ph 3
(a) (b)
Figure 17. Olefin metathesis reaction and mechanism. (a,b) Grubb catalysts.
The mechanism involves a [2,2] cycloaddition between a transition metal alkylidene com-
plex and the olefin, resulting in an intermediate metallocyclobutane [117]. The metallocycle
breaks in the opposite way to give a new alkylidene and a new olefin. Repeated exchange at
the metal results in an equilibrium mixture of olefins, usually as an equilibrium mixture of
cis- and trans-isomers. The reaction is used in the petrochemical industry to modify hydro-
carbon structure, using catalysts such as WCl6 /SnMe4 or Re2 O7 /Al2 O3 . These catalysts are
less active when other functional groups compete for the active site, and the application of
metathesis in oleochemistry has the paralleled development of novel catalysts, such as Grubb
catalysts, containing sterically hindered metal alkylidenes (Figure 17a,b).
Self-metathesis describes the reaction of an unsaturated fatty acid with itself. For example,
methyl oleate gives a mixture of starting material (50%), unsaturated hydrocarbon (25%), and
long-chain unsaturated diester (25%), all as a mixture of cis-and trans-isomers. (Figure 18).
The diester can be converted to the musk component civetone, but a more efficient route is
through self-metathesis of the ketone oleon derived from methyl oleate by Claisen condensa-
tion [118] (Figure 18).
Cross-metathesis of an unsaturated fatty ester with a normal alkene is a versatile way
of producing chain-shortened or chain-extended homologs leading to oleochemicals with
chain lengths outside the C16 –C22 range of most commodity oils. Methyl oleate reacts with
hex-3-ene, in large excess to suppress self-metathesis and push the reaction toward the C12
ester and hydrocarbon products. Ω-Olefins may be chain extended similarly, the ethene
produced being removed to drive the reaction to completion. Cross metathesis provides a
route to compounds otherwise difficult to obtain, for example, triacontanol from reduction
of the product from methyl erucate and 1-octadecene. Ethenolysis (cross-metathesis with
COOMe × 2
+
MeOOC
COOMe
oleon
Re2O7/SiO2,Al2O3/Bu4Sn
civetone
Figure 18. Self-metathesis reactions.

NOVEL CHEMISTRY FOR FUNCTIONALIZING THE ALKYL CHAIN 33
ethene) produces shorter chain Ω-olefins with a wide range of applications. A high pressure
of ethene is used to force the reaction to the desired products. Ω-Olefins produced either
by metathesis or from pyrolysis of castor oil can be coupled to give long-chain dibasic
acids [119].
Metathesis of intact oils produces polymeric products resulting from intra- and intermolec-
ular bond formation, and they can be used to produce high-viscosity stand oils from drying
oils without the loss of double bonds that occurs on thermal polymerization. Vegetable oils
can be metathesized efficiently at low temperature and pressure using Grubb’s ruthenium
catalyst (Cy3 P)2 Cl2 Ru CHPh, without the rigorous exclusion of water and oxygen required
with WCl6 /SnMe4 [120]. Pretreatment of the oil with silica gel may be required.
As a reaction with 100% atom efficiency achieved at moderate temperature (<100 ∘ C) using
renewable resources, metathesis has potential in a sustainable chemical industry. A recently
developed catalyst (Figure 17b) has an efficiency that justifies industrial application in the
production of fine chemicals [120]. The hydrocarbon by-products of metathesis, for example
α-olefins, are also valuable starting materials. Metathesis in oleochemistry, in the context of
green chemistry, has recently been reviewed [121].
8. NOVEL CHEMISTRY FOR FUNCTIONALIZING THE ALKYL CHAIN
Oils and fats are renewable resources for the chemical industry. Increasing the range of
oleochemicals that can be produced could add value to existing crops and provide a market
for new crops, driving research into novel fatty acid derivatives. Most current oleochemical
production involves reaction at the carboxyl group, with the chain length and unsaturation of
the alkyl chain chosen to give the desired melting behavior or hydrophobicity. Introducing
functionality to the alkyl chain through radical, electrophilic, nucleophilic, pericyclic, and
transition metal-catalyzed addition to carbon–carbon double bonds leads to novel compounds
with commercial potential. Only a small selection of recent research is illustrated here,
focusing on three promising approaches: neighboring group participation, Friedel Crafts
acylation, and free-radical addition reactions.
Functionalizing the alkyl chain places more emphasis on the structure of the fatty acids
used as feedstock. Model reactions use single fatty acids, often monoenes with particular
double-bond positions. Large-scale use of these reactions needs oils rich in single fatty
acids to maintain the purity of the product and minimize wasteful side reactions. Suit-
able feedstocks may be current crops such as high oleic or high erucic varieties or new
crops with unusual fatty acids. Petroselenic acid (18:1 6c) from Umbelliferae oils and
5-eicosenoic acid (20:1 5c) from meadowfoam oil are of particular interest as distinc-
tive products can result from neighboring group participation. Breeding to increase the
monoene content of some oils may be desirable. 𝜔-Olefins are useful starting materials;
10-undecenoic acid is available from pyrolysis of castor oil, and others may be produced
by metathesis (see Section 7.4). Recent, wide-ranging reviews of this area are available [4,
5, 122].
8.1. Neighboring Group Participation

Neighboring group participation is the involvement of a nearby functional group in the reac-
tion of another functional group. It may influence the regioselectivity of the reaction or lead to
OH
HClO4
CH2Cl2
O O
HX ROH
H+ Lewis acid
OH O OR O
X OR
14 14
Figure 19. Neighboring group participation leading to lactones and other products from Δ5 acids.
X = OH, RO, or RNH.
specific products, often as a result of cyclization to five-and six-membered rings. Neighboring

group participation reactions of fatty acids were reviewed recently [123] and can be used
to introduce mid-chain functionality, including heterocyclic groups. Double bonds and the
carboxyl group usually react independently of each other, but Δ4 and Δ5 bonds may inter-
act with the carboxyl through neighboring group participation leading to γ- and Δ-lactones
(five- and six-membered rings, respectively). The Δ5 acids from meadowfoam oil readily form
lactones when refluxed with perchloric acid. The proportion of Δ- and γ-lactones depends on
the solvent: 6 : 1 in hexane and 40 : 1 in dichloromethane. The Δ-lactone is formed faster, but
the γ-lactone is the more thermodynamically stable isomer. High dilution and a nonparticipat-
ing polar solvent that stabilizes the intermediate cation favor kinetic control of the reaction
[124]. The lactones can be ring opened by treatment with water, alcohols, and amines in acid,
giving 4- and 5-hydroxy acids, esters, and amides [125]; alternatively, treatment with an alco-
hol and a Lewis acid catalyst under more vigorous conditions results in an alkyl group ether
linked to the chain [126] (Figure 19).
8.2. Friedel Crafts Acylation

Friedel Crafts acylation with an acyl chloride and Lewis acid catalyst is more often associated
with aromatic compounds. Ethylaluminium dichloride (EtAlCl2 ) is an effective catalyst for the
acylation of aliphatic olefins, including fatty acids and alcohols, giving β,γ-unsaturated ketones
[127]. The reaction occurs with both terminal and internal double bonds, with the acyl group
becoming attached to one of the double-bond carbons while the double bond migrates one car-
bon. Reaction at terminal olefins is regiospecific with addition to the terminal carbon giving a
linear product and a predominantly trans-double bond. Internal double bonds give an approx-
imately equal mixture of trans-regioisomers (Figure 19). α, β-Unsaturated acid chlorides give
allyl vinyl ketones that undergo Nazarov cyclization to prostaglandin- and jasmonate-like
molecules (Figure 20) [128]. Neighboring group participation in petroselenic acid (18:1 6c)
NOVEL CHEMISTRY FOR FUNCTIONALIZING THE ALKYL CHAIN 35
O O
11
+
OH R Cl
10
EtAlCl2
O
9
R
OH
10
O
COOH
10 9
Cl
EtAlCl2
O
O
11
COOH
10
(+ regioisomer)
H3PO4/HCOOH
O
COOH
(+ regioisomer)
Figure 20. Friedel Crafts acylation reactions.
leads to intramolecular cyclization [129]. Friedel Crafts acylation is a flexible route to new and
highly functionalized oleochemicals containing reactive allyl keto functions [129].
8.3. Free Radical Addition Reactions

Double bonds participate in free radical addition reactions, and these can be of synthetic
use in introducing functional groups [130]. A particularly simple reaction is the prepara-
tion of γ-lactones by solvent-free addition of 2-halocarboxylates to fatty esters, catalyzed by
commercial copper powder at 100–130 ∘ C [131]. Iodides are most reactive and can be prepared
in situ from more readily available bromides and sodium iodide (Figure 21).
Perfluoro alkyl iodides add to both terminal and internal double bonds when the reaction is
initiated by electron transfer from metals such as finely divided silver, copper powder, and lead
with copper acetate. Using an 𝜔-olefin and a perfluoroalkyl-α, ω-diiodide, a perfluoro group
can be inserted into a long-chain compound [132] (Figure 21). Deiodination of the product
by catalytic reduction results in highly hydrophobic alkyl chains with interesting surfactant
properties.
O
11
+ COOMe
OH
10
I
Cu
OH
O
O
O
11
2 OMe + I(CF2)nI
10
Pb/Cu(OAc)2
I I
(CF2)n
MeOOC COOMe
7 7
H2
Pd/C
(CF2)n
MeOOC COOMe
Figure 21. Radical addition reactions.
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Chemistry of Fatty Acids

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Chemistry of Fatty Acids

2. COMPOSITION AND STRUCTURE

2.1. Fatty Acids

Fatty acid Common name Formula Chain length

4:0 Butyric CH3 (CH2 )2 CO2 H Short

Fatty acid Significant sources

4:0 Butter, dairy fats

Fatty acids with trans or non-methylene-interrupted unsaturation occur naturally or are

Almond 0.09 0.07 6.8 2.3 0.09 9.3 67.9 22.8

Typical midrange values are shown; the balance is minor components.

(a) (b) (c) (d)

Fatty acid Averaged melting point Methyl esters

8:0 16.3 −38.6

Source: Adapted from [137] and data was from [138–147].

CH2OH sn-1 (α) CH2OOCR P

Stereospecific numbering Triacylglycerol

Figure 3. Structure and stereospecific numbering of acylglycerols.

PPP POP PPO OPP POO OOP OPO OOO

1-palmitoyl-2-linoleoyl-3-oleoyl-sn-glycerol is abbreviated to PLO or drawn as shown in

TABLE 6. Contrasting triacylglycerol composition of some commodity oils [Molecular Species

Cocoa butter Coconut Lard Olive Soybean

2.3. Bulk Properties

3. HYDROLYSIS, ESTERIFICATION, AND ESTER EXCHANGE

SEa SV IV Unsaponifiable matter

Butter 242–267 210–232 26–40 <0.5

RCOOR′ + H2O RCOOH + R′OH (1)

RCOOR′ + R′′COOH R′′COOR + RCOOH (3)

TAG + glycerol MAG + DAG (5)

3.3. Ester Exchange Reactions

3.4. Lipase-Catalyzed Reactions

4.1. Autoxidation and Photooxidation

4.1.1. Autoxidation Autoxidation is a free-radical chain reaction, involving a complex

4.1.2. Photooxidation Light, in the presence of oxygen, promotes oxidation of unsatu-

4.1.3. Decomposition of Hydroperoxides Allylic hydroperoxides are reactive molecules

A R′′CHO + R′CH CH•

B R′CH CHCHO + R′′•

Figure 7. Decomposition reactions of allylic hydroperoxides.

a halocarbon or aromatic solvent, in the presence of bicarbonate to neutralize the carboxylic

An oxygen bridged manganese complex was recently reported to catalyze double-bond

4.4. Oxidative Cleavage

COOH HOOC COOR

Figure 12. Alternative oxidative cleavage reactions.

5.1. Hydrogenation of Double Bonds

5.2. Catalytic Partial Hydrogenation

5.3. Production of Fatty Alcohols

6. PRODUCTION OF SURFACE-ACTIVE COMPOUNDS AND OLEOCHEMICALS

6.1. Nitrogen-Containing Compounds

TABLE 8. Routes to nitrogen-containing surfactants.

RCH2 NH2 + CH2 O → (reduction) → RCH2 NMe2 Tertiary amine

ROH + SO3 → ROSO3 H

RCH2 COOH3 + 2SO3 → RCH(SO3 H)COOSO2 OCH3

Figure 14. Alkyl polyglycoside. Degree of polymerization = y + 1.

6.5. Carbohydrate-Based Surfactants

6.6. Dimers and Estolides

7. MODIFYING FATTY ACID STRUCTURE

Isomerization and conjugation change the properties of natural methylene-interrupted fatty

Figure 16. Alkali-induced conjugation of methylene-interrupted olefins.

7.3. Chain Shortening and Extension

7.4. Olefin Metathesis

Figure 18. Self-metathesis reactions.